NAN La THERMODYNAMICS ° fa] mi tan ~ iS hs THR OUMGe EXAMPLES @ ba Om tteUniversities Press (India) Private Limited Registered Office 35-819 Hyderguda, Hyderabad 500 029 (A.P.). India Distributed by Orient Longman Private Limited Registered Office 3-6-752 Himayatnagar, Hyderabad 500 029 (A.P.), India Other Offices Bangalore / Bhopal / Bhubaneshwar / Chennai Emakulam / Guwahati / Hyderabad / Jaipur / Kolkata Lucknow / Mumbai f New Delhi / Patna © Universities Press (India) Private Limited 2003 First print 2003 Reprinted 2005 ISBN 81 7371 423 1 All rights reserved. No part of this book may be reproduced of transmitted in any form or by any means, electronic or mechanical, including photocopying, recording or by any information storage and retrieval system, without permission « in writing from the publisher, Typeser by S.K. Typesetters Printed in India at ‘Sree Kalanjali Graphics, Hyderabad 500 029 Published by Universities Press (India) Private LimitedContents Chapter 1 Basic Concepts 1-62 Chapter 2 Zeroth Law of Thermodynamics 63-74 Chapter 3 Properties of Simple Compressible Fluids 75 = 136 Chapter 4 First Law of Thermodynamics 137 = 236 and its Applications Chapter 5 Second Law of Thermodynamics m= Chapter 6 Thermodynamic Potentials and Avalibility 328 = 363 Chapter 7 Thermodynamic Relations 364 = 420 Chapter 8 Power and Referigeration Cycles 421-504 Chapter 9 Nonreacting Gas Mixtures and Psychrometry 505 — S66 Chapter 10 Combustion and Chemical Thermodynamics S67= 654 Appendices 655 — 680 - Nomenclature 681 — 688 Index 689 — 694Urheberrechtlich geschiitztes MaterialBasic Concepts Example 1.1 List some of the main activities of an engineer and how are they related to a study of thermodyna Solution > ‘The main activities of an engineer are concerned with : 1, The design and development of new processes or the improvement of the existing processes. 2. To use the available resources namely space, material, energy and time in an optimal way. That is, the processes are to be designed such that they require minimum energy, space and material to perform the required task. Example 1.2 An engineer who is entrusted with the task of producing methanol according to the reaction CO (gas) + 2H, (gas) + CH,OH (liquid) would like to know the answers to a few questions, before he undertakes the design and development of a process. some of the questions which can be answered by a study of thermodynamics. Solution : Application of thermodynamic principles would provide solutions to the following questions. 1, Whether the anticipated reaction is feasible or not at the specified temperature and pressure. . If the reaction is feasible, to what extent the raw materials can be converted into products or what is the degree of conversion ? nENGINEERING THERMODYNAMICS THROUGH EXAMPLES 3. Is it possible to alter the degree of conversion by changing the pressure and temperature at which the reaction is taking place ? 4. Is it possible to increase the degree of conversion by controlling the ratio of reactants while they are fed to the reactor ? 5. How much energy is required to change the state of the reactants to the desired pressure and temperature ? 6. How much energy is required to separate the desired product from the byproducts and reactants ? 7. How much energy is required to carry out the reaction ? Example 1.3 Thermodynamics can be studied by adopting either a macroscopic or a microscopic approach. Distinguish between macroscopic and microsocopic approaches. Solution : Thermodynamics can be studied by adopting two different approaches, namely, macroscapic ana microscopic. In the macroscopic approach, the state of matter is described by specifying only a small number of variables and these variables can be measured or estimated, For example, the state of a gas enclosed in a container can be described by specifying the pressure (P), temperature (7) and volume (V), all of which can be easily measured. Inthe macroscopic approach the structure of matter under consideration is not taken into account. That is, the state of a gas, liquid or solid can be described by specifying the variables like P. Tand V. All matter consists of a large number of microscopic particles called atoms and molecules. In the microscopic approach the structure of matter or the state of agregation, like gas, liquid or solid is taken into account, The atoms or molecules, constituting the matter, move at random with independent velocities and there exist intermolecular attractive and repulsive forces. In the microscopic approach, the state of matter is described by specifying the position and velocity vectors of each of the constituting atoms or molecules and the intermolecular forces that ‘exist among them. Thus, in the microscopic approach a large number of variables are required to describe the state of matter and these variables cannot be directly measured. A knowledge of the structure of matter is essential in analyzing the behavior of the matter. The macroscopic approach is adopted in the study of classical thermodynamics whereas the microscopic approach is adopted in the study of statistical thermodynamics.BASIC CONCEPTS Example 1.4 For a thorough understanding of any science it is essential to have a good knowledge of the units of measurement. Every system of units adopts a few base units. What are the base units in the International System of units.? Solution : ‘The base units adopted in the International System of units (or SI units) are : Kilogram (kg) for mass; metre (m) for length ; second (s) for time ; Kelvin (K) for temperature; mole (mol) for quantity of matter ; ampere (A) for electric current and candela (cd) for luminous intensity. Example 1.5 Define the base units (a) metre (b) second (c) Kelvin and (d) mole. Solution : 1. Metre (m) ; In 1960 the General Conference on Weights and Measures (Conterence Generale des poids et Measures, abbreviated as CGPM) defined the metre as the length equal to 1,650, 763.73 wavelengths, in vacuum of the radiative transition between 2p,, and 5d, in krypton - 86, 2. Second (s): The CGPM 1967 defined the second as the duration of 9 192, 631, 770 periods of the radiation corresponding to the transition between the two hyperfine levels of the ground state of cesium - 133 atom. 3, Kelvin (K): The CGPM 1967 defined Kelvin as equal to 1/273.16 of the thermodynamic temperature of the triple point of water (0.01°C). The relation between the Kelvin scale of temperature and the Celsius temperature scale is given by K=C+273.15 4. Mole (mol): The CGPM 1971 defined the mole as the amount of substance which contains as many elementary entities as there are atoms in 0.012 kg of carbon - 12. The number of clementary entities in one mole is equal to the Avogadro's number 6,022 045 x 10°". When the unit mole is used it is necessary to specify the elementary entities as atoms, molecules, ions, electrons etc. Example 1.6 What are the principal features of the SI units ? Solution + Allthe physical quantities are classified into two groups as primary quantities and secondary quantities. The primary quantities are measured in terms of theENGINEERING THERMODYNAMICS THROUGH EXAMPLES. base units and the secondary quantities are measured in terms of derived units. The principal features of the SI units are 1. Minimum number of base units (only seven) are used to cover the field of science and engineering. 2. Based on the definitions or physical laws, the derived units are obtained in terms of base units. The derived units do not contain any arbitrary constants. 3. The familiar derived units have been given internationally accepted names. 4. Multiples and submultiples of units have been recommended to facilitate the use of SI units to cover a wide range of values. Example 1.7 Derive the dimensions of the derived units~force, pressure, energy and power and name their ST units. Also provide the relations between the base units and derived units, Solution The Newton's second law of motion gives force (F) as the product of mass (mi) and acceleration (a), That is where L is distance and 1 is time. Units of F= kg ms = N (newton) Force has the dimensions MLT ~ The SI unit of force is named as newton (abbreviated as N) in honor of the Scientist Newton. One newton is the force required to produce an acceleration of 1 m/s? ina body of mass | kg. Pressure (P) is defined as the force per unit area. That is P=FIA kg m m Pressure has the dimensions ML~'T? The SI unit of pressure is pascal (abbreviated as Pa) and Pa = N/m? If a force F acting on a body moves it through a distance L in the direction of the applied force, then the work done (W) (ar the energy transferred to the body) is given by Units of P= =kg m-'s~? = Pa (pascal)BASIC CONCEPTS 5 WEL Units of energy = kg ms? m= kg m? 5 = J (joule) Dimensions of energy = ML? T* The SI unit of energy is joule (abbreviated as J) and J= Nm The power is the rate at which energy is consumed or delivered per unit time. That is E Power = nerey Time kgm 2 , Units of power = ———— = kg m?* W (walt) s Dimensions of power = ML? T-* The SI unit of power is watt (abbreviated as W) and W = J/s Note The S] units newton, pascal, joule and watt which are named after the farrous scientists are abbreviated using the capital letters N, Pa, J and W. AU other units ave abbreviated using the lower case letters, Example 1.8 What are the accepted prefixes in SI units to express large and small quantities 7 Solution The internationally accepted SI prefixes are given below. Factor — Prefix Symbol — Factor Prefix Symbol 10 deca da lo! deci d 102 hecto h 107 centi e 10 kilo k 107% milli 10° mega M 107% micro ao lo? giga G 10" nano n 10! tera T 1o-!2 pico Pp 10!5 peta P to's femto 10" exa E 1o-* atte aENGINEERING THERMODYNAMICS THROUGH EXAMPLES Example 1.9 ‘What conventions are recommended by CGPM to express the SI units and quantities? Solution : The following conventions are recommended by CGPM to express the ST units and quantities, 1. The symbol of a prefix should be combined with a single unit symbol forming a new symbol. For example 1000 « Pa = kPa. 2. Compound prefixes should not be used to express a quantity. For example 10° m cannot be written as | m pm (milli micro metre), but should be expressed as I nm (nanometre). 3. The SI base unit for mass is kg which already contains the SI prefix k (for kilo). Therefore, 10 kg can be expressed as | mg and notas | pkg. 4. Except at the end of a sentence, a period (.) should not be used after a symbol of an SI unit. 5. Capital letters should not be used is SI units while writing in full, except atthe beginning of a sentence. They should be written as pascal, newton, joule etc. 6. The unit symbols should not be used in plural form. It is incorrect to write 150 Js for 150 joules but it should be written as 150 J. 7. The unit symbol should be placed after the numerical value, leaving a space in between the numerical value and the unit symbol. 8. Care should be taken to avoid confusion between the SI prefix milli (m) and the base unit metre (m) while expressing a quantity. For example, mN is used for millinewton, where as m N is used to express (metre x newton), Similarly ms stands for millisecond while m s indicates (metre x second), 9. When a unit, is obtained by multiplication or division of two or more units, they can be indicated as shown below: newton x metre = Nm metre + (second)? = nvs* or ms 10, The SI prefixes should be selected such that the numerical value lies between 0.1 and 1000. For example, 101 325 Pa can be written as 101.325 kPa or 0.101 325 MPa; 5500A (= 5500 x 10-* cm) can be written as 550 nm. However, when the values are presented is a tabular form, for the same quantity, it is advisable to use the same SI prefix throughout even if some of the numerical values lie outside the range 0.1 to 1000,BASIC CONCEPTS: Note 7 Il. While writing 2 quantity with several digits, to facilitate reading, they should be separated into groups of three, counting from the decimal point towards right and left, These groups should be separated by a small gap and should not include a comma. Example 1.10 Ifa long glass tube closed at one end is completely evacuated and the open end is immersed in a pool of mercury, keeping the glass tube upright, the mercury rises in the glass tube. At ane standard atmospheric pressure, the mercury rises, toa height (1) of 760 mm, If the acceleration due to gravity (¢) is 9,806 65 v/s? and the density (p) of mereury is 1.339 51 10" kg/m’, what is the value of the standard atmospheric pressure in SL units ? Selttion + The pressure exerted by the column of mercury, which is balanced by the standard atmospheric pressure is given by ky P = phe = 1.359 51x wr «760 mm x h(x 9.806 65 ("| m 1000 mm ors (4 = 101 325.01 Pa= 101. 325 kPa 1. The St unit of pressure (Pa) is quite small in magnitude and hence for convenience it is customary ta express pressure in kilopascal (kPa) or imegapaseal (MPa). 2. There are certain units which are outside the S1 and are recognised because of their practical convenience. They are I litre (2) = 1 x 10% cin*; I bar = 105 Pa = 100 kPa, 3. The pressure exerted by | millimetre column of mercury is named as Torr Usually subatmospheric pressure or pressure below atmospheric pressure iy expressed in Torr standard atmospheric pressure =101.325 kPa = 1.013 25 bar = 760 Torr I Torr = 133.322 Pa Example 1.11 Express the following quantities as indicated.ENGINEERING THERMODYNAMICS THROUGH EXAMPLES (a) 300,000,000 W in kW and in MW (6) 10 kPa in bar and in Torr (c) 20 dm in litre and in m* (d) 2A in pm and in om (e) 1 gem’ in kg/m? (M 0.15 J in kJ and in mJ Solution : (a) 300,00,000 W = 300,000 kW = 300 MW 3 (b) 10 kPa= ee =0.1 bar a 10 kPa = 10%10_ 133,322 ( Pa _\_75.006 Tor Pa/ Tor 3 (c) 20. dm' = 20 dmx (ox) =20x10° cm’ =20! im 4 20 dm? = 20 dm* x (2) =0.02m" dm (d) 2A=%A) x 10% (St) ae) -2x10" in cm =2x 104 pm=0.2 nm g g 1 (kg cm y 3 3 82] x——| “8 |x| 100" | = 1010? kg/m? lon (5) oa m O'kgrm (f 0.15 J= 0,000 15 kJ = 150 mJ) Example 1.12 According to Newton's universal law of gravitation, the force (F) between wo bodies of masses m, and m, which are separated by a distance £ is given by mm F=G Te where G = 6.672 « 10-!! Nm? kg™, is the universal gravitational constant.BASIC CONCEPTS 8 (a) Given that the radius and mass of earth are 637] km and 5.9659 x 104 kg respectively, estimate the acceleration due to gravity on earth. (b) Given that the radius and mass of moon are 1738 km and 7.35 x 102 kg respectively, estimate the weight of an astronaut of mass 70 kg on moon. (c) Determine the ratio of the acceleration due to gravity on earth to the acceleration due to gravity on moon. Solution : (a) Let m= mass of a body. Gravitational force acting on the body, F = one =meg A yt 4 . 9659 x | or po ole 6.672 107"! x 5.9659 x 10 = 9.8066 ms? R (6371 «10° (b) Weight of the astronaut = Force exerted by the astronaut as a result of gravitational force field GraM , _ 6.672% 107"! x 70x7.35 x 107 =113.64N Ro (1738x108)? _ GM, _ GM, (©) ean = Be Breen = Re 2 24 2 Ben _ Me (4) _ 5.965910 4 38) 6 R,) 7asxio™ “\ea7i) = Sinoon m Example 1.13 An experiment is designed to correlate the volumetric flow rate of fluid through a pipe of uniform cross section with the pressure drop across a specified length of the pipe. In this experiments a U-tube manometer with mercury (p = 1.3595 x 10‘ kg/m?) is used to measure the pressure drop of a fluid, the density of which is 800 kg/m*. At a particular flow rate, the difference in the levels of mercury in the two limbs is 20 cm. Determine the pressure drop. Solution : The mercury manometer is shown in Fig.E 1.13. Atthe surface S-S, pressure is the same. Hence pressure exerted by the fluid in the left limb AS is identical to the pressure exerted by the fluid in the right limb BS. That isENGINEERING THERMODYNAMICS THROUGH EXAMPLES: Pat Py B+ D = Py 8) +P, Bh P,— P= gh (P,,~ Pp) = 9. 81 X 0.2 x (1.3595 x 10*— 800) = 25.104 kPa or s-- Wl (HAM LEELA Fig.E 1.13. Sketch for Example 1.13. Example 1.14 The atmospheric pressure is due to the air surrounding the earth. Assuming that the air behaves like an ideal gas (P = p RT) where p is molar density, mol/ mm and the atmospheric air has a uniform temperature T, derive a relation to estimate the pressure as a function of altitude. Solution + (P+aP)A pagan | | pa Fig.E 1.14. A differential volume element of the atmospheric air.BASIC CONCEPTS: Note vi Consider a differential volume element of the atmospheric air as shown in Fig.E 1.14 and apply the force balance to obtain (P+ dP)A+MpAgdh=PA where Af is the molar mass of air or “IP = gMpdh eat 8 or fun = oRT pPdP 0 Mtg di P -RT he Tin (PrP) ° h Me ‘ or Example 1.15 What is molar mass ? Assuming that atmospheric air is a mixture of nitroven and oxygen in the mole ratio 79:21 estimate the molar mass of Selution + The mass of one mole of a substance is called molar mass, Basis : | mole of air. N, present in air = 0.79 mol and O, present in air = 0.21 mol Molar mass of Nitrogen = 28 x 107' kg ; Molar mass of Oxygen = 32 x 10° kg Molar mass of air = 0.79 x 28 x 107% +.0.21 x 32 x 10 = 28.84 x 10 ke The molar mass of air is usually seken as 28.97 x 107 kg because af the presence of small quantities of CO, and argon, Example 1.16 Define a thermodynamic system and state its characteristics.12 ENGINEERING THERMODYNAMICS THROUGH EXAMPLES Solution : A definite quantity of matter (which is enclosed by a boundary that separates it from the rest of the universe) on which we focus ourattention for thermodynamic analysis is called a thermodynamic system. The important characteristics of a system are: . Asystem contains a definite quantity of matter . This quantity does not undergo any change as the system undergoes a process. Therefore, a system is sometimes called as Control mass. 2. The boundary enclosing the system may be real (for example the glass wall of a thermos flask acts as a boundary for enclosing coffee (system) contained in the flask) or imaginary (for example one may focus his attention on air contained in 1m x 1m x Im space of a room). 3. The system boundary may be rigid or may change its shape, as well as in during a given process. That is the volume of'a system may undergo a change. 4, The system may exchange energy either in the form of work or heat or both, with its surroundings or with other systems. If a system does not exchange energy, in the form of work as well as heat, with its surroundings it is called an isolated system. 5. A system may be very simple, like a certain quantity of coffee held in a thermos flask or it may be complex like a huge petrochemical plant. 6. The choice of a system is not unique and it depends on the analyst. Note All matter external to the system is called surroundings, The combination of a system and its surroundings is called universe. Example 1.17 What are the essential features of a thermodynamic property.? Solution : A thermodynamic property is a characteristic which can be used to describe the state of a system. The essential features of a property are: 1. Athermodynamic property should have a definite value when a system is in a particular state. 2. The change in the value of the property should not depend on the path followed by the system in reaching the specified state. In other words, theBASIC CONCEPTS 13 change in the property depends on the initial and final states of the system only. That is the change in the property Z can be written as 2 J d£=MZ= Z,-Z,. is a thermodynamic property is a point function or state function and it is not a path fuction. In other words, its differential is exact. Note If Z=Ztaxy)shen 2) dv+| 22) dy= atic + Nay i), ay J, dZ is an exact differential if f)-@8 dy), \ax), Example 1.18 For a particular thermodynamic system, the following expression has been suggested for the differential of pressure (P). ap Rat_{_Rt__2a\ 4, v-b ((w-by ov Where Tis temperature, v is volume, a, b and & are constants. Judge whether the given differential is exact or not. If it is exact find the relation between Pv and T. Solution : The given relation tells that P = P (7Z.v). Then oP oP dP= (32) r+(32) aaa Ndv (A) Where M= (@P 1aT), and N= (24) av,ENGINEERING THERMODYNAMICS THROUGH EXAMPLES The given differential for pressure is = at dp (B) ‘The given differential will be exact if and only if (3r),-(r) : Therefore, let us check whether Eqn. (C) is satisfied or not. (2 = tl) a), (vey oT), (v-by Eqn.(C) is satisfied. Hence, the given expression is an exact differential. To determine the explicit relation P= P (Tv), we can partially integrate M with respect to T and obtain p= fmdry, -[4] AT. Fe) (D) v-b Where f(v) is an integration constant, which is a function of y only. To determine the value of f (v), we can evaluate (=) from Eqn. (D) and compare it with the T (=, given value of NV or foe 2a or f= 4 (E) v r Where C is a constant which is independent of both T and v. Now, substitute for f (¥) from Eqn. (E) in Eqn. (D) to obtain. aT aye P= vbBASIC CONCEPTS 15 Example 1.19 Determine the explicit relation P= P (7, v) for Example 1.18 by partially integrating N= (| * with respect to v. av Jp Solution : -RT_ 2a RT a a ed | ne =——- A fi ldvy {|{ 2% | prt e) Aj Where 7) is an integration constant, which is a function of T only. To Pp determine the value of f(7), evaluate (2) from Egn. (A) and compare it with or the given M. “Tye +H or PDy=0 of f=C (D) Where C is a constant which is independent of T and v. Substitute the value of f(7) from Egn. (2) in Egn. (A) to obtain RT a v-b y Example 1.20 Rework Example 1.18 by simultaneously integrating both the terms to obtain the relation P= P (7, v) Solution : The given relation is (See Example 1.18) Integration of the above relation gives o= AT aT vob (A) —b16 ENGINEERING THERMODYNAMICS THROUGH EXAMPLES. Where C is an integration constant. In Eqn.{A), it is necessary to drop one of the terms which is repeated. In this case the term v= ve ar is repeated. By dropping one of the terms = in Eqn. (A) we get Example 1.21 Verify whether dZ= (Axy + 4y) dx + (207 + 8xyidy is an exact differential or not. If exact find Z = Z/a, y). Solution : dZ = (Axy + 4y*) de + (207 + Bxy) dy = Md + Ndy where Madu +45? and N=20 4 8xy If dZ is an exact differential it must satisfy the condition ().-(30), Therefore, let us check whether the above condition is satisfied or not. oM a 2 (F). = 5 dart ay) sare By av) _ ais _ (2 } = g,2r +80) = 4r+8y Therefore Eqn. (A) is satisfied. Hence dZ is an exact differential To determine Z = Z/x,y), one can partially imtegrate M war.tx. or N witty. Integrating M partially w.rt.x. we get Z= [Max = [(4xy + 49?) de = 2Py + 4ay? + fly) (8) where f(y) is a function of y only. Integrating N partially wart. y, we get Z= [Ndy = J(2.2 + 8.xy) dy =Lty + day? + ffx) (C)BASIC CONCEPTS Note where f(x) is a function of x only, From Egn. (B) we get (2) = 2x? +8xy4 f’ Uy) = N= 2x? +8 ay y Y or fy) =0 or five Where C is a constant which is independent of x and y. Hence Zadty + dye (D) Alternatively, form Eqn. (C) we get Iz 2 (2) = dayt4y' + f’'(2)= M=4ay+4y KS or £0) =0 or fly=C where Cis a constant which is independent of x and y. Hence Z=dey+4y tC Example 1.22 Distinguish between extensive and intensive properties with the help of an example. Solution : The properties which depend on the mass of a system are called extensive properties, where as the properties which are independent of the mass of a system. are called intensive properties. At NTP (normal temperature and pressure i.e. at OPC and 1 standard atmospheric pressure) one mole of a gas occupies a volume of 22.4 litres. Consider two systems A and B such that system A contains one mole of oxygen at NTP and system B contains 10 moles of oxygen at NTP. If one measures the volumes occupied by the systems A and B, it will be found that system B occupies a volume of 224 litres which is equal to ten times the volume occupied by system A, That is the volume occupied by a system depends on the mass of the system and hence volume is an extensive thermodynamic property. Measurements of temperature and pressure show that systems A and B will have the same temperature (0°C) and pressure (1 standard atmospheric pressure), That the properties P and 7 do not depend on the mass of the system and they are called intensive properties. J. The ratio of an extensive property to the mass (or the property per unit mass) is called the specific property. For example18 ENGINEERING THERMODYNAMICS THROUGH EXAMPLES Total volume _ v 3 Specific volume, v= = — = mk pect Totalmass 8 2. The ratio of an extensive property to the mole number (or the property per mole) is called the molar property. For example, _ Total volume = =m? /mol Molar volume, v= = Mole number For simplicity of notation we use v to denote, both molar volume and specific votume. The units m3 kg or m® / mol indicates whether it is specific volume or molar volume. Example 1.23 Classify the following properties. (a) pressure (b) temperature (c) volume (d)} internal energy (e) volume per mole (f) mass (¢) enthalpy per unit mass. Solution : Extensive property : (¢); (d): () Intensive property : (a); (b) Specific property : (g) Molar property : (e) Example 1.24 Assuming that the molar volume of a system depends on pressure and temperature, derive the following relation. adh > =BadT -KdP Where =) = coefficient of volume expansion P 1 & = Isothermal compressibilit: vier}, Pressibilty Solution :BASIC CONCEPTS 19 or dv 1 or) op! *) aP v var) vlaP), =BaT—xaP Example 1.25 OB) _ _f aK Show that oP), ar}, Solution Consider v=v(T, P). Then dv & = Bat -xdP (See Example 1.14] v or dv =P vd? -xKviP Since volume is a property, i following condition must be sati (ga [zw - @-@ Example 1.26 Explain the meaning of the terms differential must be exact. Therefore, the (a) kinetic energy {b) potential energy (c) mechanical energy. Solution : (a) Kinetic energy. The energy possessed by a body by virtue of its motion is called the kinetic energy. If a body of mass of m moves with a velocity V the kinetic energy (KE) possessed by the body is given by KE= nv? (b) Potential energy. The energy possessed by a body by virtue of its location or configuration is called potential energy. If a body of mass m is at an elevationNote ENGINEERING THERMODYNAMICS THROUGH EXAMPLES of above the datum plane, the potential energy (PE) possessed by the body is given by PE =mgh where g is the accleration due to gravity. A compressed spring or a stretched rubber band also possesses potential energy, (c) Mechanical energy. The sum of the potential energy and Kinetic energy of a body is called the mechanical energy of the body. 1. The kinetic energy and potential energy possessed by a body can be estimated in terms of macroscopically measurable quantities (V and h) and hence they are called macroscopic modes of energy. 2. The kinetic energy and potential energy can be completely converted from one form to the other. These are the most useful forms of energy. 3. The principle of conservation of energy for mechanical systems (proposed by Leibnitz) states that the sum of the kinetic energy and potential energy (mechanical energy) remains constant during the motion of a body. Example 1.27 An clevator having a mass of 2000 kg is moving upright and after reaching a height of 80 m above the ground level the cable holding the elevator breaks. The elevator falls freely to the ground level where it hits a strong spring and brought to rest at the position of the maximum spring compression by a locking arrangement. Assume that there is no friction between the elevator and its shaft. Calculate: (a) The potential energy of the elevator at the moment when the cable is about to break. (b) The work done on the elevator in raising it to the height of 80 m above the ground level. (c) The velocity and the kinetic energy of the elevator when it is about to touch the spring at the bottom. Solution : (a) Potential energy, PE = mgh = 2000 x 9.81 x 80 = 1569.6 KF (b) Minimum force required fo move the elevator, F = mg Work done, W = Fs = mgh = 1569.6 kIBASIC CONCEPTS 21 (c) When the cable is about to break, PE = 1569.6 kJ; Kinetic energy, KE=0 PE + KE= 1569.6 kJ) When the elevator falls freely under gravity and when it is about to touch the. spring PE = 0. Since total energy remains constant KE= 1569.6 kJ KEn mV? 2 + or v= [PRE [2xtsen sic? = 39,62 mvs m 2000 Example 1.28 Ttis required to eject a projectile of mass 2 kg from a rocket, so that it reaches to a maximum height of 300 m, Calculate the velocity with which the projectile should leave the rocket. The projectile after reaching the maximum height falls freely and on the return path it hits a tower after travelling a distance of 250 m. Calculate the velocity with which the projectile hits the tower. Solution : When the projectile reaches the maximum height, its Kinetic energy KE =0 and potential energy, PE = mgh = 2 x 9.81 x 300 = 5886 J PE + KE= 58863 While the projectile is freely falling, its total energy (PE + KE) = 5886 J Ata height of 50 m above the ground, that is after travelling 250 m during the retum path, PE=mgh=2x 9.81 x 50=981) ‘Therefore KE= 5886 - 981 = 4905 J Example 1.29 A diatomic molecule can be modelled as a system of two particles connected to each other by a spring. It is well known that the gas mc ‘ecules are not at restNote ENGINEERING THERMODYNAMICS THROUGH EXAMPLES and they move at random with independent velocities. Consider 1 cm? sample of nitrogen gas at NTP held in a rigid container resting on a table top. Considering the table top as the datum plane does the gas possess potential energy, kinetic energy, internal energy? Explain the origin of the internal energy for the gas. Solution AUNTP, the number of molecules in | cm*is approximately 10”. The sample of gas is resting on the table top. At a macroscopic level, the gas sample is not moving and hence its KE is equal to zero. Considering the table top as the datum plane, the PE of the gas sample is also equal to zero. Thus the gas does not possess any macroscopically observable modes of energy. Ata microscopic level, the gas molecules move at random, If V,, Vi and V,, denote the velocity vectors of a molecule? in x,y andz directions, the translational kinetic energy possessed by a molecule is m (V3 + V2 + V3) /2, where mis the mass of a molecule, Consider the line joining the two nuclei of nitrogen atoms as the X-axis and place the centre of mass of the molecule at the origin of the coordinate axes. Then the molecule rotates about Y and Z axis and possesses rotational kinetic energy. The rotational kinetic energy for rotation about each axis is given by .o? / 2, where / is the moment of inertia of the molecule about the centre of mass and « is the angular velocity. In addition to the translational and rotational motion of the molecule as a whole, the atoms of the molecule vibrate about their equilibrium positions. Then the molecule posseses certain vibrational energy which is associated with the vibrational motion. At a microscopic level, it is not possible to measure the translational, rotational and vibrational energies possessed by each molecule, These modes of energy are called microscopic modes of energy. Similarly any sample of gas possesses electronic energy, nuclear energy, etc. in addition to the above modes of energy. The sum of the energies associated with all these microscopic modes is called the internal energy, Therefore, the sample possesses internal energy which cannot be measured at a macroscopic level. The energy possessed by a system due to its location or configuration is called potential energy. The energy possessed by a system by virtue of its motion is called kinetic energy. A macroscopic system possesses PE, KE and internat energy (U). Then the total energy (E) of the system is given by E=KE+PE+U Example 1.30 Distinguish between steady state and equilibrium with the help of an example.BASIC CONCEPTS Solution : Suppose one end of a copper rod is kept in contact with condensing steam at 100°C while the other end of the rod is in contact with melting ice at O°C. Then energy flows through the copper rod in the form of heat from the condensing steam to the melting ice. At time r= 0, that is at the instance when the copper rod is suddenly brought into simultaneous contact with the condensing steam and melting ice, the temperature of the rod is uniform along its length. Measurement of temperature at a specified location of the copper rod reveals that the temperaiure gradually changes with time initially and attains a constant value after some time. There will be no further change in the temperature of the rod (at a spe: d location), however Jong one may observe. This observation will be true at any location of the rod and the temperature of the red continuously varies from 100°C at the condensing steam end to 0°C at the melting ice end. Then the copper rod is said to be ina steady state. Steady state implies that the properties (like temperature in this case) do not changs respect to time. In other words, the time derivatives of properties at any given location (say d7/ dt) is equal to zero in steady state Now, isolate the copper rod (system) from the condensing steam and melting ice baths and measure the temperature at amy specified location of the rod. The temperature gradually c| undergo any further cl along the length of the od indicates that the temperature is uniform through out the length of the rod. Then the system is said to be in a state of equilibrium. In a state of equilibrium, the m has no tendency to undergo any further change. Equilibrium is a concept associated with the absence of any tendency for further change on a macroscopic level. The tendency to change occurs due tothe presence of driving forces (like temperature difference). Thus equilibrium implies the absence of driving forces. Ina state of equilibrium, the thermodynamic properties of a system have unique values, Example 1.31 What criteria a system should sat equilibrium’? 'y for it to be in a state of thermodynamic Solution : For a system to be in a state of thermodynamic equilibrium it should simultancously satisfy the criteria for thermal equilibrium, mechanical equilibrium and chemical equilibrium. Example 1.32 Explain the criterta for (a) thermal equilibrium (6) mechanical equilibrium and (c) chemical equilibrium,24 ENGINEERING THERMODYNAMICS THROUGH EXAMPLES Solution : (a) Tf ther no further change in the thermal condition (temperature) of a system when isolated, the system is said to be in a state of thermal equilibrium. In a state of thermal equilibrium, there is no temperature gradient within the system, Since a system in thermal equilibrium has uniform temperature, a unique value can be specified for the temperature of the system. If two systems are in thermal equilibrium with each other, the temperatures of both the systems are identical. In other words, the criterion for thermal equilibrium is given by Ty=T, where 7, and T,, denote the temperatures of the systems A and B, respectively. (6) Ifthere is no imbalance of forces in a system when it is isolated itis said to be in a state of mechanical equilibrium. Ina state of mechanical equilibrium, the system has a uniform pressure and a unique value of pressure can be specified. If two systems are in a staté of mechanical equilibrium with each other, the pressures of both systems are identical. That is, the criterion for mechanical equilibrium is given by P,=P, where P, and P, denote the pressures of systems A and B, respectively. {c) If the composition of a system does not undergo any change due to diffusion, mass transfer or chemical reaction and if there is no tendency for a change in its chemical composition when the system is isolated, it is said to be in astate of Chemical equilibrium. The difference in the chemical potential (which is defined in a later chapter) causes diffusion, mass transfer or chemical reaction. In a state of chemical equilibrium the chemical potential is uniform through out the system. Suppose two systems A and B each consisting of N components are in a state of chemical equilibrium. Then the criterion of chemical equilibrium can be stated as pA = pF, fords 1, 2... where Hi! and uP denote the chemical potentials of component i in systems A and B, respectively. Example 1.33 Suppose a rigid and insulated vessel is filled with a mixture of liquid water and water vapor at 100°C and standard atmospheric pressure. Considering the contents of the vessel as a system, is it in a state of equilibrium ? Can we say that the molecules which were originally in liquid phase continue to exist in the same phase at all times ?BASIC CONCEPTS 2 Solution : The system satisfies the criteria of thermal, mechanical and chemical equilibrium. Hence, the system is in a state of thermodynamic equilibrium. At a macroscopic level the amounts of liquid and vapor phases remain constant and the system appears to be static. However, at a microscopic level the system is not at rest. Some liquid water evaporates and some water vapor condenses. That is the molecules move from liquid to vapor and vice-versa, but at such a rate that the rate of evaporation is exactly balanced by the rate of condensation. Hence the molecules which were originally present in the liquid phase do not continue to exist in the same phase at all times, Example 1.34 An equimolar mixture of H, and O, is contained in a rigid vessel at | bar and 25°C. No detectable change in its composition has been observed over a period of 30 days. Since there is no change in the composition of the mixture can we say that the mixture is in a state of chemical equilibrium ? If not, specify why ? Solution : The mixture of H, and Q, is not in a state of chemical equilibrium, though there is no detectable change in its composition over a long period of time. The rate of reaction between H, and ©, to form water vapor at 25°C is very small and hence there is no change in the composition of the mixture. The mixture has a tendency to undergo a chemical reaction. If a small amount of energy (in the form of an electric spark or by introducing a lighted match stick) is added to the mixture to create a small disturbance, the mixture reacts violently to form water vapor. Hence the system is not in a state of chemical equilibrium, Example 1.35 Classify the states of equilibrium with the help of a mechanical analogue. Solution : Consider a sphere resting at the bottom of a spherical bowl as shown in Fig.E.1.35 (a). If the sphere is disturbed it will settle into the original state, however large the disturbance may be. This state of equilibrium, in which the system (here the sphere) returns to ils original state even if it is subjected to large disturbances is called stable equilibrium. In thermodynamics we are mostly interested in stable equilibrium states. The sphere shown in Fig.E 1.35 (b) returns to its original state if it is subjected to small disturbances but settles in a different equilibrium state if the disturbance exceeds a certain magnitude, Such a state of equilibrium is called metastable. The sphere shown in Fig.E 1.35 (c) settles intoENGINEERING THERMODYNAMICS THROUGH EXAMPLES adifferent state when it is subjected to a small disturbance and this state is called unstable state of equilibrium. @ Fig.E 1.35, States of equilibrium (a) stable (6) metastable (c) unstable. Example 1.36 With careful cooling it is possible to cool water to a temperature (say 10°C) below its normal freezing point. The cold water produced in this manneris usually called super cooled water. Is the super cooled water in a state of equilibrium? Solution : Consider the super cooled water as a system and let us apply the criteria of equilibrium to judge whether it is in a state of equilibrium or not. The system has a uniform temperature and hence it satisfies the criterion of thermal equilibrium. The system also satisfies the criterion of mechanical equilibrium since the pressure is uniform through out the system. The system contains pure water with uniform temperature and pressure. Hence the chemical potential is uniform through out the system. Thus it satisfies the criterion of chemical equilibrium also. Since the system simultaneously satisfies the criterion of thermal, mechanical and chemical equilibrium, itis in a state of thermodynamic equilibrium. If the system is subjected to a minor disturbance cither by adding a small amount of dust or by shaking the container, the supercooled liquid immediately freezes into ice. Hence, the system is in a state of metastable equilibrium. Example 1.37 What is a process ? Solution : When a system changes from a specified initial equilibrium state to another equilibrium state, the path followed by the system in reaching the final equilibrium state from the given initial state is called the process. Example 1.38 Explain the meaning of Quasi-Static process.BASIC CONCEPTS: 7 Solution : A process which takes place very slowly and with infinitesimal driving force is called a quasi-static process. Suppose a gas at pressure P is enclosed in a piston cylinder assembly. If the piston is restrained by an external force such that the external pressure on the piston is (P - dP) where dP > 0, then the gas can expand slowly. Such an expansion occurs at a slow rate and the system appears to be almost static. Then the process followed by the gas is quasi-static Example 1.39 What is meant by a reversible process ? Explain it with the help of an example. Solution A process which proceeds with no driving forces is a reversible process. As an example consider a gas which is enclosed in a frictionless piston cylinder assembly, as shown in Fig.E1.39. Suppose the piston is loaded with a certain mass of fine sand particles. If the sand particles are moved one after another on to adjacent platforms, the piston moves up slowly and the gas expands. During the expansion process, the system (here, the gas) does work on the surroundings and the sand particles are raised to different clevations as shown in Fig.E1.39 (5). If the sand particles one after another are restored on to the piston from the adjacent plaforms, the piston moves down slowly and the gas gets compressed. During the compression process the work done en the system is exactly equal to the work done by the system during the expansion process, Thus the process can be carried out in either direction. By reversing the direction of the process both the system and surroundings are restored to their respective jal states. Then the process undergone by the system is reversible. During a reversible process the system is always in a state of equil surroundings. CELL Sand Particles Platforms (a) () Fig.E 1.39, Reversible Process.Note ENGINEERING THERMODYNAMICS THROUGH EXAMPLES A reversible process is a quasi- static process, but a quasi-static process need not be a reversible process. Example 1.40 . State the mechanics definition of work done by a force. Apply the mechanics. 2 definition of work and show that the work done by a gas is given by | Pav 1 Solution ; In mechanics work done by a force is defined as the product of the force and the displacement in the direction of the applied force. That is the differential work done (dw) is given by dw = Fds . where F is the applied force and ds is the differential displacement. Consider a certain amount of gas contained in a cylinder piston assembly as shown in Fig.E 1.40. At time r let P be the pressure of the gas inside the cylinder. x v, Vv (b) Fig.E 1.40, Sketch for diagram 1.40. Schematic representation of work done by a gas.'The system (enclosed by the dotted line) constitutes the gas contained in the cylinder. (b) Representation of work done an a P-V diagram. The shaded area represents the work (a 2 done Jrav by the gas, 1 Ina differential time dr, let the piston of cross—sectional area A move a differential distance dL while the motion of the piston is opposed by an external pressure (P —dP) where dP —> 0. Then, the differential work done by the gas is given byBASIC CONCEPTS: dW = Eds = (PA).dL = P (AdL) = Pdv 2 or We f Pdv 1 {t may be noted that the external pressure (P — dP) is always infinitesimally smaller than the gas pressure. Hence the expansion process can be reversed at any time by increasing the extemal pressure infinitesimally more than the gas pressure. That is, if the external pressure is (P + dP), the gas undergoes a compression process. During the expansion/ compression of the gas the forces ‘on the moving boundary are balanced and hence the process is reversible. The process can be represented on a P — V diagram as shown in Fig.E 1.40. Example 1.41 Suppose a piston cylinder assembly initially contains a gas at pressure P, and occupies a volume V, and it is allowed to expand reversibly rill it attains a pressure P,. Is it possible to calculate the work done by the gas from a knowledge of its initial and final conditions ? Explain whether work done by a gas is a property of the gas or not. Solution : From the given data the initial (P,,V,) and final (P,,V,) states of the gas are known. The work done by a gas is given by v, v Y, Fig.E 1.41. Representation of two different reversible processes between the specified initial and final states of the gas. The arca under the curve 1A2 represents the work done by the gas, if it follows the path A. The area under the curve 12 represents the work done by the gas if it expands along the path B.30 ENGINEERING THERMODYNAMICS THROUGH EXAMPLES We fav i To integrate the above relation, one should know the relation between the pressure (P) and volume (V) of the gas during expansion/compression process. That is the path followed by the gas must be known to evaluate the work done. Fig.E 1.41 shows two different reversible path 1A2 and 1B2 connecting the given initial and final states of the gas. Since [Pdv represents the area under the curve the work done during path 1A2 is different from the work done during the path 1B2. In other words, the work done depends on the path followed by a system. Hence, it is not possible to evaluate the work done purely froma knowledge of he initial and final states of a system. The work done by a system is a path function and hence it is not a property of a system. Work is an interaction, that is energy transfer, between a system and its surroundings. Hence work is energy in transit. Example 1.42 A piston-cylinder assembly contains one mole of an ideal gas at (P_,v,.7,)- If the gas expands reversibly such that (a) the final volume is V, while the pressure is held constant (2) the final pressure is P, while the temperature is held constant and (c) the final pressure is P, while Pv?= constant during expansion. Here y is the ratio of heat capacity at constant pressure to the heat capacity at constant volume. Determine the work done by the gas. Solution : (a) The work done by the gas is given by We | Pdv a For constant pressure expansion, the above relation reduces to 2 w=P fav=P, @,-¥) I (b) We know that for an ideal gas Pv = RT. If the temperature of the gas is held constant, we get Pi, = Py, = RT, Then the work done by the gas is given byBASIC CONCEPTS: Hn 2 z 2 we frdv = [lay arf” = RTIn 2 i i v 1 v yu (ce) The path followed by the gas during the expansion process is. Pv? = constant or Pv? = Pav? = K = Put or P=KvT The work done by the gas is given by Koplow ty _ I-y 2 2 wa | Pav = [ KyYdv = 1 1 _ Pvp eehyt RyRy y-i yr Example 1.43 Tt is desired to compress one mole of air (ideal gas with y= 1.4) from | bar and 27°C to 10 bar and 27°C, For this purpose compare the work to be done for the following processes : (a) Isothermal compression. (b) constant volume heating followed by a constant pressure compression and {c) adiabatic compression (PV = Constant) followed by constant volume cooling. Solution : (a) The isothermal compression process is shown as 1 A2 on the P-v diagram in Fig.E 1.43 ‘The work done for the isothermal process | A2 is given by 2 2 = = far - Re A Win [pa = fare = RTIn® = RT In 1 = 8.314 x 300 x In — x xin 7 =-5.7431 kd32 ENGINEERING THERMODYNAMICS THROUGH EXAMPLES 1 bar 1 Reversible isothermal process: Fig.E 1.43. The isothermal compression process is shown as 1A2. The path 1B2 shows the constant volume heating foltowed by constant pressure compression. The path C2 shows adiabatic compression followed by a constant volume cooling. (b) The work done along the path 1B2 is given by a 2 Wing = Wip + Wp = | Plo | Pade 1 g = 0+ Pry vg) = Py(vy “woe -4| ¥2 fe Blemb8m(-8 =sa14c300(1-) == 22.4478 kJ (since T, = T, and Pv = RT) The work done along the path 1C2 is given by c 2 Wige Wie +We,= | Pdv+ | Pav 1 Cc -fMicfeve 9 - fic fey y-1 y-lBASIC CONCEPTS: 33 Prt = Pat =P (since V.= V,) yy a or Poe a u ] v Fu Peg wi (since F, = 1) ji A 1 ¥ ro -n{] vs ayn 3) (2) Therefore, W,c)= ———*#4— = ——12 iat . y-l y-l 0. Note — The negative work done by the gas indicates that wark is ta be done an the gas by the surroundings. Example 1.44 A piston-cylinder assembly contains air (ideal gas with y= 1.4) at 200 kPa and occupies a volume of 0.01 m*. The piston is attached to one end of a spring and the other end of the spring is fixed to a wall. The force exerted by the spring on the piston is proportional to the decrease in the length of the spring from its natural length. The ambient atmospheric pressure is 100 kPa. Now, the air in the cylinder is heated till the volume is doubled and at this instant it is found that the pressure of the air in the cylinder is 500 kPa. Calculate the work done by the gas. Solution : We know that the force exerted by the spring on the piston is given by (V-Vy) A Where i = spring constant Fo=KX=K34 ENGINEERING THERMODYNAMICS THROUGH EXAMPLES: A =cross—sectional area of piston Vy = Volume of air if the spring is at its natural length, that is the spring is neither compressed nor elongated. V= Volume of air if the spring is compressed by a distance X, Py 001 Vm 0.02 (a) (b) Fig.E 1.44 (a) Sketch for Example 1.44. (b) P-v diagram in which shaded area represents the work done. Force acting on the piston due to ambient atmosphere is given by Fi=P,A Force balance on the piston when the air volume is Vis given by KW -%) A PA=PLA or p=p.+Kw—w) (A) wt 0. Force balance on the piston in the initial state gives P\ASPAtK (%%) (B) Force balance on the piston in the final state gives P,A=PA+ «(4o) (c)BASIC CONCEPTS The work done by the air is given by We | fdx=f PAdX = [Pdv 2 K K J fr +Sw-vhav= Puls M45 [0a MOP -Vr} ' K = FalVa VIF As Vo) (Vi = Vad HLM Vo (Mi ~ Vodt K 2A? = PCV, — Vt Ms +, — 2¥a (Va VY) K = {ret et +H 2409} 2-¥9 (D) 24 From Eqns. (B) and (C), we get PtP, oS 2 Substituting Eqn.(E) in Eqn. (D), we obtain = Pat Eat M-Mp) (E) we BB, 4) _ (200% 10° + 500x 10") 2 ‘The shaded area of the trapezium ABCD in Fig.E 1.44 (b) represents the work done by air. It can be observed that the area of the trapezium ABCD is given by X (0.02 - 0.01) = 3.5 kJ P+P, aw Example 1.45 A balloon which is initially collapsed and flat is slowly filled with hydrogen at 100 kPa so as to form it into a sphere of radius 1m. Determine the work done by the gas in the balloon during the filling process. Solution : During the filling process, the gas pressure remains constant at 100 kPa. Therefore, the work done during the constant pressure process is given byci ENGINEERING THERMODYNAMICS THROUGH EXAMPLES Parry 3 2 Ws Jrav= PU W)= Px Seis -A)= 1 _ 100x108 x4nxP - 3 (Since r, = 0 when the balloon is collapsed and flat) = 418.88 kJ Example 1.46 ‘One mole of a Van der Waals gas undergoes a reversible and isothermal expansion from the initial volume V, to the final volume V,, Determine the work done by the gas. Solution : The Van der Waals equation of state is given by a RT a (p+S}o-m= RT or Paw ‘The work done by the gas is given by w= [roel 5 )ar-nrn{actl {tt} Example 1.47 One mole of air (ideal gas with y = 1.4) at pressure P, and temperature 7, is compressed at constant volume (ill its pressure is doubled. Then it is allowed to expand reversibly and isothermally to the original pressure and finally restored to the original temperature by cooling at constant pressure. Sketch the path follawed by the gas, on a P—V diagram and calculate the net work done by the gas, Solution : Fig.E 1.47 shows the path followed by the gas on P-v diagram. The net work done by the gas is given by W= W,, + W,, + Wy, = feav {pave [pas 1 2 a = 04 RT; InS+ ROH)BASIC CONCEPTS a7 Isothermal process Fig. 1.47, Path followed by the gas on Pv diagram. 1-2 is a constant volume process, 2-3 is isothermal process and 3-1 is a. constant pressure process. For an ideal gas AM 282 Ror the path 1-2, v, =v,. Hence, 1 2 7e = 27, (Since P, =2A) 1 For the path 1-3, pressure is constant, Hence P, = P,, Therefore Fin A BH ge ye RAY o Be sey 7 TT “ TA (Since 2-3 is a constant temperature process.) Then the net work done by the gas is given by W= RT Int + ly 14) = RIF, In + Ry = 204) ¥» 4 = 2RT\In 2-2A,y, = 2RT, In2-2 RT, = 2RT;(In2-1) Example 1.48 Is it possible to view the expansion of a gas ina piston—cylinder assembly as the one and the only one effect external to the system (the gas contained in the cylinder) as the raising of a mass against the gravitational force? If so devise a means to view such an effect.Note ENGINEERING THERMODYNAMICS THROUGH EXAMPLES Solution = System FigE 1.48 To visualise the work done by the gas enclosed in a piston cylinder assembly as equivalent to raising of a mass in a gravitational field. ‘Yes, It is possible to modify the surroundings, such that the one and the only one effect (sole effect) external to the system is the raising of a mass against the gravitational force as shown in Fig.E 1.48. One can generalize and state that all mechanical work done by a system is equivalent to raising of a mass, through a certain distance, in a gravitational field. Example 1.49 ‘Suppose the terminals of a storage battery are connected to an electrical resistor through a switch. When the switch is closed electrical current flows through the resistor, the resistor becomes warm and the charge of the storage battery decreases. ‘Consider the storage battery as a system and apply the mechanics definition of work to identify whether work is done by the system or not. Is it possible to modify the surroundings such that the sole effect external to the system is equivalent to raising of a mass ? If so devise a method. Solution : In mechanics work done is defined as the product of the force and the displacement in the direction of applied force. When the terminals of a storage battery are connected to an electrical resistor, current flows through the resistor, thereby decreasing the charge of the battery. In the interaction between the battery and the resistor, no force has moved through any distance and hence the work done by the battery from the mechanics point of view, is zero. We know that an electric current is a manifestation of the flow of electrons which are driven by an electrical potential difference. The electrons are crossing the boundary of theBASIC CONCEPTS 39 system (battery) and some work is done in moving the electrons. However, the mechanics definition of work fails to identify the work done, ‘Switch Motor + - Storage battery Fig.E, 1.49, Visualization of battery interaction as equivalent to raising of a mass. It is possible to modify the surroundings such that the sole effect external to the system is equivalent to raising of a mass as shown is Fig.E 1.49. The resistor can be replaced by an electric motor which draws the same amount of current as the resistor, One can wind a string around the shaft of the motor and suspend a mass through this string. When the switch is closed the motor runs and winds the string which in turn raises the mass. Example 1.50 State the thermodynamic definition of work. Solution : In thermodynamics work done by a system on its surroundings is defined as that interaction whose sole effect, external to the system, is equivalent to raising of a mass through a certain distance. Example 1.51 Consider a certain amount of liquid contained ina vessel. A paddle wheel or stirrer is inserted in the liquid and the stirrer is rotated, for some time, by lowering a mass as shown in Fig.E 1.51, While the mass is lowered work is done on the liquid. Is it possible to define the work done on the system as the interaction whose sole effect, external to the system, is equivalent to lowering of a mass ? Explain. Solution + It is not correct to state the thermodynamic definition of work done on the system by its surroundings as the interaction, whose sole effect, external to the system is equivalent to lowering of a mass. The system (liquid) is initially at40 ENGINEERING THERMODYNAMICS THROUGH EXAMPLES some state, say at temperature 7, . After performing work on the system, by rotating the stirrer, the system reaches a different state—say at temperature T,,. Now, leaving the system untouched, the surroundings can be modified as follows. The stirrer and the mechanical arrangement to rotate the stirrer can be removed and the vessel can be placed on a hot body to raise the temperature of the liquid from T, to T, as shown in Fig.E 1.51 (6). The modifications have been made external to the system only and we find that the energy of the hot body (possibly its temperature also) is reduced, even though the system has undergone the same change as depicted in Fig.E 1.51 (a). That is, lowering of a mass is not the sole effect external to the system. The state of the system can be changed by either of the methods shown in Fig.E. 1.51 (a) and (b). Hence in thermodynamics, the work done on the system by its surroundings is not defined in terms of lowering of a mass. (a) (b) Fig E 1.51, (a) Work done on system by lowering a mass. (b) Energy transfer as heat to the system from a hot plate. Example 1.52 The work associated with the boundary movement (expansion / compression work) is given by [PdV. Is there a situation where Ws [Pav Solution : The work done during a reversible process is given by We [Pav If the process is irreversible, the work done is not equal to [PdV, Suppose a vessel is divided into two compartments I and 2. The compartment | of volumeBASIC CONCEPTS: a” V, contains a gas at pressure P, and the compartment 2 is evacuated. If the partition separating the compartments is removed, the gas expands and occupies the entire volume of the vessel. Let P, and V, denote the final pressure and volume of the gas. The pressure and volume of the gas have changed. To calculate J Pd¥, a knowledge of initial and final values of pressure and volume are not enough. It is necessary to know the variation of pressure and volume during the expansion of the gas. To obtain some information regarding the intermediate values of pressure and volume, the expansion process can be carried out in steps as shown in Fig.E 1.52. Suppose several movable partitions A, B, C, D, E are placed in compartment 2 (a) Compartment 2 Fig.E 1.52 (a) Vessel divided into two compartments 1 and 2. ‘Compartment | contains a gas at P,. V, while the compartment 2 is evacuated. The two compartments are separated by a partition 1. Movable partitions A, B, C, D, E are placed in compartment 2. (b) P-Vdiagram showing the intermediate values of pressure and volume when the partitions A, B,C, D, E are removed one after another. If the partition | is removed, the gas in compartment | expands and moves upto partition A, at which instant the gas pressure is P, and its volume is V,,. If the partition A is removed, the gas expands and its state is given by P, and V,. Similarly one can remove the partitions B,C, D and E and measure the pressure and volume of the gas after removing each partition. A plot of P versus V then will appear as shown in Fig.E 1.52 (b). It is possible to evaluate the area underENGINEERING THERMODYNAMICS THROUGH EXAMPLES 2 the curve | ABCDE 2 (Shaded area in Fig-E 1.52 (b)) to determine Jpav. However, this value does not represent the work done by the gas. In reality, the gas has not done any work since no force has been moved. Such an expansion is called free expansion, that is an expansion which is not restrained by any force. During the expansion of a gas, the work done is equal to zero. In this case or in a situation which is not reversible, the work done Wis not equal to [ PdV. Example 1.53 Is there is situation where dV =0 and yet dW #07 Solution = Yes. It is possible to have a constant volume (dV = 0) process and yet the work done is not equal to zero. Suppose a piston cylinder assembly contains a cerain amount of gas and the piston is held in position with the help of latches. Now it is possible to introduce a paddle wheel as shown in Fig-E 1.53 (a) in the gas space and rotate it by performing work. It is also possible to introduce an electrical resistor in the gas space and pass electric current through it by connecting the resistor to a storage battery as shown in Fig.E 1.53 (b). In this case, the battery does work on the system (gas and resistor). Since the piston is held in position, there is no change in the volume of the gas (dV = 0) and yet dW #0. Battory System (ay (6) Fig.E 1.53, Illustratation of process to show that dV = 0 and yet dW #0. (a) paddle wheel (or shaft) work done on system (b) Electrical work done on system.BASIC CONCEPTS: 43 Example 1.54 One made of work is associated with the movement of the boundary of the system and it is usually called expansion/compression work. Are there any other modes of work interaction between a system and its surrounding 7. If so, specify some of them. Solution + There are several modes of work interaction between a system and its surroundings. Some of the common modes ef work interaction are Compression / expansion (boundary movement work) Extension of a solid rod (elastic work) Spring work Stretching of a liquid film Work transmitted through a shaft or shaft work Electrical work Polarization Magnetization Example 1.55 Derive a relation to estimate the work done if an elastic rod is subjected to tension. Solution : Consider an elastic rod of length L and cross—sectional area A, which is fixed at one end as shown in Fig.E 1.55 as the system. Cross sectional area =A Fig.E 1.55. Elongation of an clastic rod.ENGINEERING THERMODYNAMICS THROUGH EXAMPLES. The elastic rod is fixed at ¥ = 0 and a force F is appliea at the other end. If o is the normal stress acting at the other end of the rod, then the force F acting on the rod is given by F=oA Asa result of the applied force, if the rod is elongated by dr, the work done by the elastic rod is given by dW=-Fde=-oAdx or ow --0t ode where € =— = elongation per unit length = strain cle V=AL = Volume of the rod A negative sign is introduced in the above relation to take into account that work is to be done on the rod if dx is positive. The work done per unit volume: (WIV) of the rod is given by To integrate the above relation it is essential to have a knowledge of the relation between stress (c) and strain (€). If the elastic rod is isothermally elongated the stress and strain are related by the Youngs isothermal modulus (Y,) which is given by If the elongation of the rod occurs in the Hooke’s law region ¥, is a constant or o = ¥,e. Then the work done is given by 2 Ww 2 y =~] ode =-[¥, ede = Le} - 23 v ! Ip ede= ee -B) or w= Zed-e) Example 1.56 One end of a steel rod of | cm in diameter and 50 cm in length is fixed and a force is continuously applied at the other end in a direction which is parallel to the length of the rod. Calculate the work done by the force on the steel rod to change its length by | cm. Also calculate the stress and force applied on the red. The Young's modulus of steel is 2 x 10" Nim?,BASIC CONCEPTS 45 Solution : The work done by the steel rod is given by w= 4g} -e) (A) 2 2 Initial volume of the steel rod = v= "4 = noo nes = 3.927 x 104 m* Youngs modulus of steel = ¥,= 2x 10!! Nim? Initial strain = €, = 0 *21 Lom L 50 Substituting these values in Eqn. (A), we get Final Strain = €, = 5 W=-2x 10"! a x (0.02)? = — 1.5708 kJ Stress = 0 = Y,€=2x 10!' x 0.02 54x 10? Nim? = 3.1416 x 10°N 2 Fore= F=o A= 4x10) «S02 Example 1.57 ‘One end of steel rod of | cm in diameter and 1 m in length is fixed to the ceiling of a roof and the other end is connected to a hook to which a mass of 10000 kg is suspended. If the Young’s modulus of steel is 2 10"! N/m? calculate the elongation of the rod and the work done on the steel rod. Solution : Force acting on the steel rod = F = mg = 10000 x 9.8 = 98 kN F_ AF _4x98x10" Stress ===" = = 1.2478 x 10° Nfm? And? (0.017 _8 _ 1.247810" ¥ 2x10 Elongation =x =€ L= 6.2389 x 107 x 1=6.24 mm Strain =¢ = = 6.2389 x10ENGINEERING THERMODYNAMICS THROUGH EXAMPLES Work done on the steel rod = —-W = re -e}) (A) Volume of the rod = ¥ = ——— ut 5 ‘Therefore wi eee (6.2389 x 1073)? = 305.71 J Example 1.58 Derive a relation to calculate the work done by a spring when it is subjected to compression or extension. Solution : To change the length of a spring either by compression or extension, it is necessary to exert a force which causes a displacement X. The displacement X of a spring is given by (L-L,) where L is the length or the spring under compression J extension and L, is its natural length or the spring length when it is neither under compression nor extension. The force exerted by the spring or the restoring force is ina direction to restore the spring to its equilibrium position. The restoring force F, is given by F,=-KX=~-K (L-L,) The negative sign indicates that the force is always opposite in direction from the displacement of its free end. Unstressed spring Extended spring Compressed spring Fig.E 1.58. A spring under compression / extension.BASIC CONCEPTS: a7 Fig.E 1.58 shows a spring under compression and extention. The work done by the spring is given by x, x, We frax=-(xxax= K(X} - X}) x x, Example 1.59 It is required to apply a force of 500 N to the free end of a spring to stretch it by 5 cm from its relaxed length. (a) Calculate the spring constant and the work done on the spring. (b) Now the spring is connected to a block and it is allowed to retum slowly such that the final length of the spring is 1 cm more than its natural length, Calculate the work done by the spring. Solution : (a) Restoring force, F=-500N Displacement, X=0.05m Spring constant, K= SE SR © S0KN Im =-62.5) —_ext 2 Work done by the spring , W = AEE = 50X10 00.05)" Work done on the spring (-W) = 62.5 J zl (b) Work done by the spring, W = —K (X3 - X}) = Stxs0x 10°00? =(0.05)?} = 60) Example 1.60 Suppose a liquid film is held between a wire frame, one side of which can be moved with the help of a sliding wire as shown in Fig.E 1.60. The interfacial tension or surface tension which is the force per unit length normal to a line on the surface is given by 1. Obtain a relation to estimate the work done on the liquid film when the surface area of the film is stretched,ENGINEERING THERMODYNAMICS THROUGH EXAMPLES Solution = . The force F applied on the liquid film by an extemal agent is given by, FH=2Lt The factor 2 is included because two film surfaces act on the wire. If the sliding wire is to be displaced by a distance dX, the external agent must do work on the liquid film. Rigid wire frame Liquid fitm Fig. E 1.60, Liquid film held between a rigid wire frame. Then the work done by the liquid film which is the negative of the work done by the external agent is given by x; x, W=- frax =- fotxax x x Associated with the displacement dX there is a change in the surface area of the liquid film. The change in the surface area (dA) of the liquid film is given by dA =2 LdX Then the work done by the liquid film can be rewritten as Xs Ay We ~ [2txdx =~ [rdA=—w4,~A)) x A Example 1.61 An aqueous soap solution is maintained in the form of a thin film, on a wire frame as shown in Fig.E 1.61. If the surface tension of the liquid is 72.75 mN/m calculate the work ‘done when the movable wire is displaced by 1 cm in the direction indicated.BASIC CONCEPTS 43 Salution : The work done, = W=~t {A,-A,) Ay— A, = 2L(X,-X,)= 2x 0.02 (0.03-0.02)=4% 10 a? Therefore W = —72.75 x 103 x 4x 10% =-29.1 x 10%] ‘The negative work indicates that work is done on the liquid film. Movable wire FigE. 1.6!. Sketch for Example 1.61 Example 1.62 tabl surface Calculate the work to be done on 1 em’ of mereury (which is av spherical drop) to disperse it into fine droplets of 4 [um diameter. 7 tension of mereury is 487 mN/m. sa Solution : Applying the principle of conservation of mass, we get pV,=NpV; or where V, = volume of the initial drop V, = volume of the final droplet = (4/3) rr," Vy, 1x10 N= 3x10" ~n(2x10%)* te) Total surface area of the droplets, A, = N (4 1 r,*) = 3x 10! x 4 (2 x 10}? = 1.508 m?ENGINEERING THERMODYNAMICS THROUGH EXAMPLES: us Sa of (Si) (= ] = 6.235107 m? 3 4n an Initial surface area of mereury, A, =4 tr)? = 4m x (6.235 103)? = 4,885 x 107 m? Work done, W =~ 1 (A, ~A,)=— 487 x 107%(1.508 - 4.885 x 10“) =- 0.73425 Work to be done on mercury = 0.7342 J Example 1.63 Power Transmission through a rotating shaft is a common engineering practice. Derive a relation to determine the power transmitted through a rotating shaft. Solution : Suppose a shaft of radius r is fixed at one end and a force F, is tangentially applied at the other end as shown in Fig.E 1.63. EX. ce <}- Fig.E 1.63. Torsion of a shaft. ‘The torque applied to the shaft = t= Fr The application of the torque results in angular displacement d9 of the point at which the torque is applied. The linear displacement, ds = nl 6 Work done, dW= Fds=F rd @ =% dOBASIC CONCEPTS. ST 8 We fre a Power transmitted, P= wv. +40 =H dt dt where © is the angular velocity (in radians) of the shaft. Example 1.64 Mixing and stirring of fluids is usually done with the help of a paddle wheel ‘or stirrer, A paddle wheel consists of a shaft to which paddles or blades are attached. When a torque is applied to the shaft, the fluid forces on the paddles balance the applied torque and the shaft rotates at constant speed. Determine the power ‘transmitted through a shaft to a liquid if the applied torque is 2 Nm and the shaft rotates at a rate of 600 revolutions per minute. Solution + The power transmitted through the shaft, P= T © Angular velocity, @ = 2th where 1 = number of revolutions per second. Therefor, P=1 0 =t2 nn =2 x 2m x 600/60 = 125.66 W Example 1.65 It is required to raise a body of mass 100 kg to a height of 60 m in the earth's gravitational field, where the acceleration due to gravity is 9.81 m/s*. Calculate the work to be done on the body. Solution : In the earth's gravitational field, the force acting on a body of mass m is given by F = mg. To raise the body, the external agent must apply a force F in a direction which is opposite to the direction of acceleration due to gravity. Then the work done by the external agent is given by We JFds= Jjmede =mgz = 100 x 9.81 x 60 = 58.86 kJ Example 1.66 The acceleration due to gravity as a function of elevation above the sea level is given by g = 9.81 — 3.32 x 10° z where g is in m/s? and z is in meters. AENGINEERING THERMODYNAMICS THROUGH EXAMPLES satellite with a mass of 300 kg is put in an orbit at an elevation of 400 km above the earths surface. Calculate the work done an the satellite. Solution : Work done on the satellite, W= J mgdz 300 (9,81-3.32 x 10~ z) dz o = J (2943 = 9.96 x 10-2) dz = 29432 - 9.96 x 1047/2 o 4 2943x 400 x 105 — ae (400 x 10°)? = 1.0976 GI Example 1.67 Derive a relation to estimate the work to be done on a body of mass m in accelerating it from an initial velocity V, toa final velocity V,. Solution : When a body of mass m is acted upon by a force F, its acceleration a is related to the force F by the Newton's second law of motion. The Force F acting on the body is given by F=ma=mdV /dt Then the work done on the body is given by Wy vi-vi We J Fds= fm (dV /dt) ds = f m(ds/dt) dV = f m VdV =m 2 vi Example 1.68 120 kJ work was done on a car in accelerating is from an initial speed of 10 km/h to 100 km/h. (a) Determine the mass of the car. (b) What could be the final speed of the car if the work done on the car is 200 kJ ? Solution ; a : 10x10° (a) Initial velocity of the car, V, = ———— = 2.778 m/s 2 Final velocity of the car, V,= 00x10" = 27.778 msBASIC CONCEPTS 53 Work done, w fmv3 -W) or 120 x 103 = zm {(27.778¥ -(2.778)7} = 381.95 m or m =314.18kg 1 (b) Work done, W= mv: -V?) 3 or 200 10°= = Be (v3 -(2.77877} or V, = 35.79 mls = 128.8 knvh Example 1.69 Suppose the terminals of a storage battery are connected to an electrical resistor through a switch as shown in Fig.E 1.69. When the switch is closed, the battery discharges doing work. Derive an expression to calculate the work done by the battery. Resistor Switch Storage teeeeeenne : ‘System Fig.E 1.69, Discharging of a storage of battery through a resistance. Solution : Consider the storage battery as the system. The electric current flowing through the resistor is a manifestation of the flow of electrons. Work is required to displace the electric charge across the boundary of the system. We may recall that the electrical potential at a point is defined as the work done on a unit charge in moving it, which is at infinite distance, to that point. The electric current is defined as the rate of change of charge. That is electric current iis given by54 ENGINEERING THERMODYNAMICS THAOUGH EXAMPLES dQ, _. a dQ. =idt i Where Q, = electric charge If the differential charge dQ, is transferred during a differential time dr with a potential difference V then the work done is given by W= -VdQ, or W=—-[V¥dQ,=- [Vide If the charge leaves the system dQ, is negative and the battery does work on the surroundings. On the other hand if dQ, is positive, that is during the charging of a battery, work has to be dene on the system. To take this into account a negative sign is introduced in the above expression. Example 1.70 Anclectric potential difference of 230V is maintained across a 47042 resistor for a period of 10 minutes. Determine the electrical work done and the power. Solution : Current i= (where R is electrical resistance) Work done, W = ViAt = 230 x 0.4894 x 600 = 67,537 kJ (Note that dQ. is negative is this case) Vi = 230 0.4894 = 112.56 W Example 1.71 A 12 V storage battery is charged by supplying a current of 2A for 3 hours. Determine the work done on the battery and the quantity of electric charge transferred. Solution : Work done, W = -ViAr = -12 x 2X3 x 3600 =-259.2 kJ Work done on storage battery = 259.2 kJ Electric charge transferred to battery, Q, = i Ar = 2 «3 x 3600 = 21600 coulombs Example 1.72 Potential energy can be stored in a spring by stretching it. Similarly one can store energy as potential energy in an electric field and the device used for thisBASIC CONCEPTS. 55 purpose is called a capacitor. In the present electronic age the capacitors play a vital role. Develop an expression to calculate the work done in charging a capacitor, Solution : A parallel plate capacitor shown in Fig.E 1.72 consists of wo parallel conducting plates of area A separated by a distance d. When the capacitor is charged, its plates have equal but opposite charges +Q, and — Q,. Usually, the charge of a capacitor is represented by Q_. Since the plates are conductors, they are equipotential surfaces-that is all points on a plate are at the same electric potential. The potential difference V between the plates is given by V=Ed (A) where E is the electric field. ‘The charge Q, and the potential difference V for a capacitor are proportional to each other. That is @.=cV (B) where C is the capacitance of the capacitor. From electrostatics we know that Q,=€,EA (c) ‘Where €, is the permittivity constant and is given by £, = 8.85 x 107? c7N m? = 8.85 x 10°? Faraday/m From Egns. (A) to (C) , we get A C= oF (D) Capacitor tedtte ‘Switch Battary Fig.E 1.72. Charging a capacitor.ENGINEERING THERMODYNAMICS THROUGH EXAMPLES: To charge a capacitor work must be done by an external agent. Starting with an uncharged capacitor, electrons are to be removed from one plate and transferred to the other plate. The electric field which builds up in the space between the plates is ina direction to. oppose further transfer. Therefore, as charge accumulates on the capacitor larger amount of work has to be done for further transfer of electrons. The differential work dW done in transferring a differential charge dQ, through a potential difference V is given by dW = -VdQ. = ~Sag, = ~ 2 VO “ Wa JQdo.=Fe=-F ‘Since work is done on the capacitor in charging it.) Example 1.73 A parallel plate capacitor is charged to 230 V. Given that the capacitance of the capacitor is 10 WF, calculate the work done in charging the capacitor. Solution : Work done in charging a capacitor is given by 2 The charge transferred Q. in given by Q.=CV=10 x 10 x 230=23 x 104 C we ¥Qe , 2302310" 2 2 = 0.2645] Example 1.74 Suppose a thin toroidal ring of material is covered with winding as shown in Fig.E 1.74. Let A be the cross=sectional area of the substance, L the mean circumference, N the number of windings and / the current passing through the winding, Develop a relation to estimate the work done in magnetising the material. Solution + From Faraday's law of electromagnetic induction the induced electromotive force £ in the winding (or back emf) is given by E=-NA (2) dtBASIC CONCEPTS s7 Fig.E 1.74. Magnetic work done on a toroidal ring. where B is the magnetic field. During the differential time dr if the differential quantily of charge dQ, is transferred in the circuit, then the work done is given by iB 10, ; dW= Blg,=- NATO, = ~wa{ 222 )an =-NAidB (A) Ina toroidal winding the magnetic field intensity (H) is given by Ni =— B L (By Substituting Eqn. (8) in Eqn. (A), we get dW =-ALHdB =-VHdB (c) where V = AL = volume of the material. The action of a magnetic field on the substance is to produce magnetization (or magnetic moment) M. The total effect of the current in the winding is to establish the magnetic field and magnetization of matter within the field. The effect is called the magnetic induction B and is given by B=, (H+M) (Dp) where M is the magnetization per unit volume and Hy is the permeability of free space. From Eqns. (C) and (DB), we get dW = —,VHdH — 1 ,VHdM (E) The first term on the RHS of Eqn.(£) represents ihe work done in increasing the magnetic field in the volume V of the empty space and the second termENGINEERING THERMODYNAMICS THROUGH EXAMPLES represents the work done in increasing the magnetization of the material by the amount dM. Therefore, the work done in magnetization (of a material) is given by dW=-1,VHdM ot on =~ pHa! (F) The negative sign indicates that work is done on the system (material to be magnetized), Example 1.75 Curie's law for paramagnetic substances is given by M = CH/T where C is Curies constant, Calculate the work done per unit volume of a paramagetic substance in changing the magnetization from M, to M,. Solution : The work done for magnetization is given by dW = ,VHdM or ae Hy) dM or =n finane=uy f Tt an -—40L cae - m9) My M; Therefore, work to be done on the substance = a (MG ~My) Example 1.76 In mechanics work done (dW) is given by the relation dW = Eds where F is the force which is an intensive parameter and ds is the displacement, which is an extensive parameter. [s it possible to generalize the above relation so that it is applicable to all modes of work interactions? If so,give a summary of the relevent forces and displacements. Solution : The work done for boundary movement (compression /expansion) is given by dW= PaV, where Pis an intensive parameter and dVis an extensive parameter. The elastic work done is given by dW/V=—-ode where the stress 6 is an intensive parameter and the stain (€) is an extensive parameter. Similarly for all modes of work the work done by a system can be generalized asBASIC CONCEPTS: 59 dW = F,.dX, where F, = generalized force, which is an intensive parameter dX,, generalized di isplacement, which is an extensive parameter . The extensive and intensive parameters associated with several modes of work interac summarized below. Generalized Work Interactions Work mode Jeneralized force Generalized Equation for work fintensive) displacement (dW =) (Extensive Boundary mation Pressure (P) Volume Pav (Compression/Expansion) Elastic Stress (a) nf e ~oule (Extension of solid) Spring Force (F) Displacement (dX) FX Surface Surface tension t Surface area dA) =tlA (Liquid film) Shatt work ‘Torque (t) Angular displacement rl (Torsion) (8) Electrical Voltage (V) Charge (dQ,) =v, (Reversibte vel) ‘apacitor Potential difference (VY) Charge(dQ ) Vd, (Electric polarization) Magnetization Magnetic field (H) Magnetization(dAf =, Hat (Magnetic polarization) Example 1.77 Name the different modes by which the energy of a system can be changed. Solution Consider a gas enclosed in a piston ~cylinder assembly as our system. The energy of the gas can be increased/decreased by compressing/expanding the gas under adiabatic conditions. That is, the energy of the system can be altered through work interaction. The energy of the gas can also be altered by cooling or heating. That is the energy of'a system can be altered through heat interaction also. Suppose an elastic rod ix considered as our system. The system's energy can be changed through elastic work as well as through heat interaction. If we consider an elastic and magnetic substance as our system, its energy can be altered by two different types of work interactions— elastic work and magnetization work in addition toENGINEERING THERMODYNAMICS THROUGH EXAMPLES: heat interaction. Now we can generalize to state that the energy of a system can be altered by two modes. They are (1) work interaction and (2) heat interaction. Example 1.78 Suppose a rigid vessel containing a gas is placed in thermal contact with a hot body. The temperature of the gas and hence the energy of the gas increases. Considering the gas as our system, identifty the interaction between the system and the surroundings from (a) macroscopic and (b) microscopic points of view. Solution + (a) Since the vessel is rigid, its volume does not undergo any change. Hence the boundary motion (compression/expansion) work is not associated with the system. Ata macroscopic level, no work interaction is responsible for the change in the energy of the system. Since there are only two médes, work and heat, by which the system can change its energy, the above interaction can be called heat interaction. (5) Ata microscope level, the atoms or molecules of the container wall vibrate vigorously since the container wall heats up when it is placed in thermal contact with a hot body. The gas consists of a large number of atoms/molecules which move with random velocities and the average velocity is proportional to ¥T. Some of the gas atoms/molecules come into collision with the atoms of the container and during the collision energy transfers from the atoms of the container to the gas atoms/molecules, Because of intermolecular collision the energy is transferred to the other atoms/motecules of the gas also, resulting in an increase in the energy of the system. During a collision, the kinetic energy of one atom/ molecule is transferred to another-atom/molecule. That is one atom/molecule does work on another atom/molecule. Therefore, ata microscope level, the energy transfer occurs through work interaction only. However, at a macroscopic level, we fail 10 observe any work interaction. Example 1.79 Explain the meaning of ‘Heat interaction’ or ‘Heat’ Solution : The mode of energy transfer which cannot be accounted as work from a macroscopic point of view is called heat interaction or simply heat, The heat interaction occurs by virtue of temperature difference across the boundary. The heat interaction depends on the path followed by a system and hence it is a path function and not a point function, Heat is energy in transit. It is not a property of the system and its differential is not exact.BASIC CONCEPTS 61 Example 1.80 ‘The two modes of energy transfer are work and heat. Does the mode of energy transfer depend on the choice of a system? Support your answer with the help of an example. Solution : ‘The mode of energy transfer depends on the choice of a system. Consider a ‘vessel containing some water, the temperature of which is raised by switching on an immersion heater (placed in water} connected to a storage battery. Suppose we consider the water alone as our system and the rest of the universe as surroundings, then the interaction between the system and its surroundings is called heat, because the energy transfer occurs by virtue of temperature difference between the immersion heater (or heating coil) and water. On the other hand, if we choose the water and the immersion heater as our system, the interaction ‘between the system and its surroundings is called work, because the energy transfer is due to the discharging of the storage battery which can be visualised as the raising of a mass, Therefore, the work and heat interactions depend on the choice of a system. Example 1.81 Consider the water contained in a container as our system. Suppose the water is initially at temperature 7, and it is allowed to interact with its surroundings. As a result of energy transfer suppose the water reaches a temperature T,, where 7, > T,. Is it possible to identify the interaction as work or heat by which the system has changed its energy? Solution : It is not possible to name the interaction as work or heat from a knowledge of the initial and final conditions of the system. The mode of energy transfer (heat or work) can be identified only while the system is interacting with its surroundings. It is possible that the container is placed on a hot body for some time to raise the temperature of the water. In such a case, the interaction is called heat. It is also possible that a paddle wheel is placed inside the water and it is rotated for sometime to raise the temperature of water. In such a case, the interaction is called work (paddle wheel work or shaft work). Example 1.82 Which of the following characteristics are true for work ? (a) Ivis a path function. (b) It is not a property of a system. (c) Its differential is not exact62 ENGINEERING THERMODYNAMICS THROUGH EXAMPLES (d) Tis not stored in a system (e) It is energy in transit. ' (f) It can be identified only during the course of interaction. Solution All these characteristics are true for work. Example 1.83 Which of the characteristics given in Example |.82 are wue for heat ? Solution : All the characteristics are true for heat.2 Zeroth Law of Thermodynamics Example 2.1 How do we characterize a thermodynamic system? Solution ; A thermodynamic system is characterized without any ambiguity by specifying certain properties.A thermodynamic system contains adefinite quantity of matter and matter possesses energy in its various forms. Therefore, a thermodynamic system is completely described by specifying some of the following quantities. *® The quantity as well as the composition of matter in terms of mole numbers of each constituent. @ The measurable properties like volume, pressure and temperature of system. * The energy of the system Example 2.2 Consider one mole of an ideal gas enclosed in a piston-cylinder assembly as a system. The system can be characterized by specifying temperature (7), pressure (P), Volume (v) etc. Are the properties 7; P and v are independent of each other? Solution : All the three properties P T and v are not independent. There exists a relationship of the form f(P v, T) = 0 among the three properties. For an ideal gas, the relationship is given by Pv = RT where v isthe molar volume and R is the universal gas constant. Only two of the three properties Rv and T can be independently varied.64 ENGINEERING THERMODYNAMICS THROUGH EXAMPLES Example 2.3 Consider a compressible substance, say an ideal gas, enclosed in a piston- cylinder assembly as the system. Is it possible to independently vary the energy and volume of the system ? Solution : Foracompressible substance, energy and volume can be independently varied, ‘The energy of a system can be varied by heat and work interactions. Suppose the piston is held in position and the cylinder can be brought into thermal contact with a hot body, transferring energy as heat to the system. Thus the volume of the system can be held constant while its energy can be changed. It is also possible to change the volume of the system by compression /expansion while the system is held at constant temperature by immersing it in a constant temperature bath. For an ideal gas, the energy depends on temperature only. Hence, the energy of the system is held constant while the volume changes. Therefore, the energy and volume of a compressible substance can be independently varied. Example 2.4 Is it possible to vary the pressure while cnergy and volume of a compressible substance are held constant? Solution : It is net possible to vary pressure while the energy and volume of a compressible substance are held constant. We know that the pressure of a gas can be changed by (a) compression/expansion (b) heating / cooling and (c) vigorous stirring. If the gas is compressed / expanded, the volume undergoes. a change even though the energy can be held at a constant value by immersing the system in a constant temperature bath..If the gas is heated / cooled in a rigid container, the energy of the system changes even though the volume is held constant. If the gas enclosed in a rigid vessel is vigorously stirred its energy increases, even though the volume is held constant. Thus we find that it is not possible to change the pressure of a gas while its energy and volume are held constant. Example 2.5 Whiat does the state postulate specify and explain its meaning. Solution : The State postulate states that for a given thermodynamic system, the number of independently variable thermodynamic properties is equal to the number of reversible work modes, associated with the system, plus one. The energy of a system can be altered by work and heat interactions. A thermodynamic system may exchange its energy by more than one workZEROTH LAW OF THERMODYNAMICS 65 interaction. A compressible substance has only one work interaction which is due to boundary movement (compression/expansion). An elastic rod can exchange its energy through one work interaction which is the elastic work, However, an elastic and magnetic substance can exchange its energy through two work interactions - namely elastic work and magnetic work. In addition to work interactions, a thermodynamic system can exchange its energy through heat interaction also, Therefore, the number of ways in which the energy of a thermodynamic system, can be changed is equal to the number of work modes associated with the system plus one. One thermodynamic property is associated with every work mode. The property v is associated with compression / expansion work mode, the property strain (€) is associated with elastic work mode and the property magnetization (M) is associated with the magnetization work mode. Hence the number of thermodynamic properties which can be independently varied is equal to the number of work modes plus one, If a given thermodynamic system is capable of exchanging its energy through n work modes, then the number of independently variable thermodynamic properties of the system is equal to (a cl). Example 2.6 How many thermodynamic properties of a system are required to describe its state 7 Solution « If a thermodynamic system has n independent variable thermodynamic properties, the state of such a system is completely described, without any ambiguity, by specifying n independent thermodynamic properties. If the independently variable thermodynamic properties of a system are held constant, no other property of that system can be varied independently. Example 2.7 Is there any limitation on the nature (say extensive or intensive) of the properties to be used in describing the state of a thermodynamic system ? Solution : There is no restriction on the nature of the thermodynamic properties that can be used to describe the state of a thermodynamic system. One can use only extensive properties or only intensive properties or a combination of extensive and intensive properties as long as they are independent of each other. Example 2.8 How many thermodynamic properties are to be specified for complete description of a thermodynamic system consisting of (a) an incompressible substance (b) an elastic substance and (c) an elastic and magnetic substance?Note ENGINEERING THERMODYNAMICS THROUGH EXAMPLES Solution : (a) Two (b) Two (c) Three Example 2.9 For a simple compressible substance which of the following sets of thermodynamic properties can be used to describe the state of the system ? (a) Energy (#) and volume (v) (b) Energy (w) and Temperature (7) (c) Energy (w) and density (p) (d) Pressure (P) and volume (v) (e) Volume (v) and density (p) (A) Pressure (P) and temperature (7) (g) Temperature (7) and volume (v) Solution + ‘The state of a simple compressible substance can be described by any of the following sets of properties, (avhs (ep): (Rv) (RIATY) If one does not insist that the energy of a system should remain constant, then one can specify the pressure instead of energy (u) as one of the independent properties to specify the state of a thermodynamic system. Example 2.10 Why is it not possible to use energy (ie) and temperature (7) or volume (v) and density (p) as a set of thermodynamic properties to specify the state of a simple compressible substance ? Solution : Energy (1:) and temperature (7) are not independently variable properties of a thermodynamic system because there exists a relation between these two properties. Similarly volume (v) and density (p) are not independent of each other. Hence one cannol use the sets. (u, 7) and (1, p) to specify the state of a simple compressible substance.ZEROTH LAW OF THERMODYNAMICS 67 Example 2.11 You may recall (from physical chemistry course) that the Gibbs phase rule can be used to determine the number to degrees of freedom (or the number of properties needed for complete description) of a system. Apply the Gibbs phase tule and determine the degrees of freedom of a simple compressible substance (like nitrogen gas) existing in gas phase. Solution : According to the Gibbs phase rule, the number of degree of freedom (F) of a system is given by 42-P where C= number of independent components P= number of phases Fora simple compressible substance (like nitrogen gas) existing in gas phase, C= land P= 1H F=C+2-Psl+2-1=2 Therefore, there are two degrees of freedom. In other words, two thermo- dynamic properties can be independently varied Example 2.12 Is the state postulate equivalent to Gibbs phase rule? What is the difference between these two? Solution : The state postulate and the Gibbs phase rule are independent. The state postulate gives the number of thermodynamic properties needed for a complete description of the state of a system. These properties can be extensive, intensive or a combination of extensive and intensive, The Gibbs phase rule gives the degrees of freedom (or the number of independent thermodynamic. properties) of a system. These properties are intensive properties only. They cannot be extensive properties. Example 2.13 State the zeroth law of thermodynamics. Solution . The zeroth law of thermodynamics states that ifeach of the two given systems. are in thermal equilibrium with a third system then the two given systems are in thermal equilibrium with each other.68 ENGINEERING THERMODYNAMICS THROUGH EXAMPLES Example 2.14 There are four laws of thermodynamics namely zeroth, first, second and third law of thermodynamics. Usually one counts starting with |. Why the counting of the laws of thermodynamic started with zero ? Solution : The first law of thermodynamics was proposed by J.P Joule in 1851 which is followed by the second and third laws of thermodynamics. During the development of the laws of thermodynamics the content or the principle involved inthe zeroth law of thermodynamics was assumed to be true without ever stating itso, However, for a logical development of the science it is necessary to state the zeroth law before presenting the other laws of thermodynamics, This was realized by R.H. Fowler in 1931. Since the other laws were formulated before 1931, counting them as first, second and third, it was necessary to call the postulate or law proposed by Fowler as the zeroth law of thermodynamics. Example 2.15 Explain how it is possible to compare the thermal state (degree of hotness) of several bodies by making use of the zeroth law of thermodynamics. Solution = A particular body called a thermometer can be brought into thermal contact with another body, say body A and allow these two bodies to reach a state of thermal equilibrium. In that state, some measurable characteristic of the thermometer - called thermometric property can be recorded. Then the thermometer in tum can be placed in thermal contact with a second body, say body B, till thermal equilibrium is established between them. Once they reach a state of thermal equilibrium one can measure the thermometric property again. If the two thermometric property readings—one measured while in contact with bedy Aand the other measured while in contact with Body B - are identical, then the two bodies A and B are in thermal equilibrium with each other. Knowing the thermal state of one of the bodies A or B, the thermal state of the other body can be determined, Example 2.16 Name a few measurements or quantities which can be used as thermometric properties. Solution : The following measurements or quantities can be conveniently used as thermometric properties in order to quantify the temperature.ZEROTH LAW OF THERMODYNAMICS 69 Length of mercury column in a capillary tube. * Electrical resistance of a wire * Pressure of a fixed quantity of gas confined ina constant volume bulb: * Volume of a fixed quantity of gas held at constant pressure. * emf generated at a junction of two dissimilar metal wires. Example 2.17 Explain the two fixed points on which the Celsius temperature scale (earlier it was called centigrade scale) is based. Solution : The Celsius scale is based on two easily reproducible fixed points, They are the ice point and the steam point. The ice point is the equilibrium temperature of the ice with water at standard atmospheric pressure and it is assigned a value of orc, The steam point is the equilibrium temperature of pure water with its own vapour at standard atmospheric pressure and it is assigned a value of 100°C. Example 2.18 At the tenth conference Generale des poids et Measures (General conference of weights and measures CGPM) held in 1954, the Celsius scale in redefined in terms of a single fixed point, What is that single fixed point? Solution : In 1954, the CGPM redefined the Celsius scale in terms of a single fixed point. The single fixed point is the triple point of water (the state in which all the three states-solid, liquid and vapor of water coexist in equilibrium) which is assigned a value of O.01°C. Example 2.19 Consider a mercury in glass and alcohol in glass thermometers. Both the thermometers are calibrated using the two standard fixed points - ice point and steam point. Suppose one measures the temperature of a body, which is approximately at SO°C, using these two thermometers will the readings be identical? Explain the reason for the discrepancy. Solution : ‘Though both the thermometers are calibrated using the same two fixed points, the values of temperature as read by both these thermometers may not be identical at any other temperature. Assuming that the variation of *he length of the liquid70 ENGINEERING THERMODYNAMICS THROUGH EXAMPLES: column is linear with temperature the scales are marked on both the thermometers. It is not necessary that the variation of the volume (or the length of the liquid column) of both liquids to be linear. Example 2.20 What is the motivation is devising an ideal gas temperature scale ? Solution : It is known that all materials do not change their thermometric properties linearly with temperature. Therefore, different thermometers, made of different thermometric materials, show different values of the temperature of a body except at the points at which they are calibrated. Hence to have reliable and reproducible values of temperatures it is necessary to devise a temperature scale which does not depend on the nature of the thermometric material. This was the basis for the establishment of an ideal gas temperature scale. Example 2.21 What is an ideal gas ? Solution : An ideal gas obeys the relation Pv = RT, where v is the molar volume and & is the universal gas constant. The value of R is 8.314 Jémol K. This equation is only an approximation to the actual behavior of gases. All gases behave like ideal gas at sufficiently low pressure (in the limit P -» 0). The internal energy of an ideal gas is a function of temperature only. Example 2.22 Describe a constant volume gas thermometer and explain how it can be used to measure the temperature of a body. Solttion A schematic diagram of a constant volume thermometer is shown in Fig.E 2.22 (a). It consists of a constant volume gas bulb which is connected to a mercury column through a mercury reservoir and flexible tube. Helium or some other gas is filled in the gas bulb and the limb AB, which has the mercury column is raised or lowered such that the mercury in the reservoir stands at the reference mark 2. Then the volume of the gas held in the bulb corresponds to the volume of gas bulb and the volume of the connecting limb up to the reference mark R. The gas bulb is immersed in the fluid, the temperature of which is to be measured, such that the entire gas bulb is in thermal contact with the fluid. Once thermal equilibrium is established between the fluidZEROTH LAW OF THERMODYNAMICS: ” and the gas, the limb AB (mercury column) is raised or lowered such that the mercury in the reservoir stands at the reference mark R. Thus the gas is held at constant volume. Then the pressure (P) of the gas is measured from the height of the mercury column, above the reference mark f in the limb AB. A lar measurement is made by immersing the gas bulb in a bath which is maintained at the triple point of water. Reference mask ‘Connecting limb —, Mercury column Mercury reservoir Flexible Tube jagram of a constant volume gas thermometer. Fig.E 2.22 (a), Schematic Let P,, denote the pressure of the gas when the gas bulb is in thermal equilibrium with the bath at the triple point temperature T,, For an ideal gas at constant volume P « 7. Therefore, T P P —_=— T=T.— a vR, (a) From a knowledge of 7,,,, one can estimate the temperature of the fluid from the above relation. The triple point temperature of water has been assigned a value of 273.16 K. Therefore, Eqn (A) can be rewritten as F T= 273.16 (8) Suppose a series of such measurements are made with different quantities and different types of gases in the constant volume gas bulb. Then the measured pressure (P) at the system temperature (7) as well as the pressures (P,) at the triple point temperature change depending on the quantity of gas in the gas bulb. A plot of T calculated from Eqn. (B) as a function of P,, appears as shown in Fig.E 2.22 (6).ENGINEERING THERMODYNAMICS THROUGH EXAMPLES: E 2.22. () Plot of 7 versus Py for a constant volume gas thermometer. It can be observed from Fig.E 2.22 (b) that the value of Tas P,,—> 0 is identical. Such a behavior can be expected because all gases behave like ideal gases as P + 0. Hence to obtain the correct temperature one should ensure that P,, is.as low as possible. Therefore to obtain the actual temperature of the system, Eqn. (8) is modified as tim | 2 T= 273.16 ial Pe Example 2.23 dtis known that the variation of electrical resistance of a wire with temperature is not linear. Is it possible to use the electrical resistance as a thermometric property ? Solution : If the variation of a thermometric property is not linear with temperature the functional dependence of the property on the temperature should be known for it to be used as a thermometric property. Example 2.24 Suppose one devises a constant pressure ideal gas thermometer for the measurement of temperature. If the measured volumes of the gas at temperature T and at the triple point of water are Vand Vv, respectively, determine the relationZEROTH LAW OF THERMODYNAMICS 73 Solution : For an ideal gas PV = nT where Vis the total volume, is the mole number of the gas. At constant pressure, the above relation gives T ~ V. , Therefore, Dov yg Ty Vip Tat, + =273:16¥. Vip hp ‘The above relation will be exact only when the gas behaves like an ideal gas or in the limit as P,, > 0. Hence, one can estimate the temperature T from the relation Vv = Lt | — T= 273.16 ny Vy Example 2.25 What are the practical difficulties »ssociated with the use of ideal gas thermometer? Solution + The ideal gas thermometer can be used at temperatures where the behavior of the gases tend to the behavior of ideal gas. It is known that at low temperatures the behavior of gases deviate from the ideal gas behavior. More over, the lowest temperature (4.2 K) can be achieved by using helium gas at its normal boiling point. This sets a limit on the lowest temperature that can be measured. In addition to this great skill and experience are required to operate an ideal gas thermometer since it is necessary to apply several corrections to obtain accurate values of temperature. Example 2.26 ‘What is IPTS-68 and name some of the primary fixed points on which it is based. Solution : In view of the practical difficulties associated with the use of idea’ thermometer, the international committee on weights and measures have adopted the International Practical Temperature Scale (IPTS-68) in 1968, based on a74 ENGINEERING THERMODYNAMICS THROUGH EXAMPLES number of easily reproducible fixed points. Some of the primary fixed points on which IPTS-68 is based are given below : Primary fixed point Temperature ("C) Triple point of hydrogen — 259.34 Normal boiling point of hydrogen — 252.87 Triple point of oxygen = 218.789 Normal boiling point of oxygen. — 182,962 Triple point of water 0.01 Nonmal freezing point of silver 961.93 Normal freezing point of gold 1064.433 Properties of Simple Compressible Fluids Example 3.1 What is meant by a pure substance ? Can we treat air as a pure substance ? Solutian : In general a pure substance is one which consists of a single chemical sp like H,O, He, N,, O,, etc. Quite often in engineering analysis one deals systems of fixed composition like air. Air is a mixture of 79 % nitrogen and 21% oxygen (by volume). If a certain quantity of air, enclosed in a piston-cylinder assembly, undergoes cooling! heating or compression/expansion processes, its composition does not undergo any change. In such cases it can be treated as a pure substance. However, if the air is cooled to sufficiently low temperatures where it can be present in both liquid and vapor phases, then it cannot be considered as a pure substance, because the composition of the liquid will be quite different from that of the vapor. Example 3.2 Explain the meaning of the term ‘phase’ Solution : A system which is uniform throughout both in chemical composition and physical state, is called a phase. A pure substance can exist in three different states of physical aggregation. For example, water can be found as solid (ice), liquid and gas (water, vapor or steam). Solids can be found in different allotropic forms. For example, sulfur can be found in rhombic form (lemon yellow in color) and in monoclinic form (orange in color). The properties of these allotropic forms differ from each other. Hence solid sulfur can be found in two different phases. Similarly solid carbon can exist in two different phases, namely- graphite and diamond,76 ENGINEERING THERMODYNAMICS THROUGH EXAMPLES: Example 3.3 Itis known that pure substances can exists in different phase. Is it possible to find mixtures also in different phases ? Give one example. Soliton : Mixtures also can be found in different phases. A mixture of alcohol and water can exist in liquid as well as vapor phases. However, the chemical composition of the vapor phase is usually different from that of the liquid phase. Example 3.4 What is meant by compressible substance 7 Solution : All substances solids, liquids and gases~change their specific ‘molar volume when they are subjected to a change in temperature and pressure. Depending on the range of the tempesature, applied pressure and on the nature of the substance the change in the volume may be significant or insignificant. If the change in the volume is negligible the substance is called incompressible, Usually liquids and solids are treated as incompressible substances. On the other hand, if the change in the volume is quite significant the substance is called compressible. Example 3.5 Define isothermal compressibility (x), isentropic compressibility (x,), and coefficient of volume expansion. (B). Solution > The isothermal compressibility (x) is defined as the rate of decrease of volume with pressure at constant temperature and per unit volume. That is. --+(%) vl ae), ‘The isentropic compressibility (k,) is defined as the rate of decrease of volume, per unit volume, with pressure at constant entropy. That is x = -1(¥ Ver), The coeffecient of volume expansion (B) is defined as the rate of change of volume, per unit volume, with temperature at constant pressure. That is (5) Vv \ar},PROPERTIES OF SIMPLE COMPRESSIBLE FLUIDS: 7 Example 3.6 Explain the meanings of the terms ‘simple substance’ ‘and simple compressible substance’, Solution : Asubstance which can exchange energy through only work mode is called a simple substance. If the work mode through which a simple substance can exchange energy is the boundary movement (or compression/expansion) then it is called a simple compressible substance. In other words, a simple compressible substance can exchange energy with its surroundings though Pdv work mode in addition to the energy exchange through heat interaction. Example 3.7 Describe the commonly employed methods by which the thermodynamic data of substances are presented. Solution : ‘The thermodynamic properties which are in wide use are pressure (P), molar! specific volume (v), temperature (7), enthalpy (h) and entropy (s) .{ The terms enthalpy and entropy are defined later]. The widely used and most convenient methods of representing the thermodynamic data are: (a) Graphical representation or presenting the data in the form of diagrams ‘or charts, (b) Tabular representation or presenting the data in the form of tables. (c) Mathematical representation or presenting the data in the form of equations. Example 3.8 Name the widely used thermodynamic diagrams for a pure substance, Solution : ‘The most widely used thermodynamic diagrams for a pure substance are: Pressure versus volume (P — v) diagram. Pressure versus temperature ( P — T) diagram. ‘Temperature versus volume (7 - v) diagram. Temperature versus entropy {7 ~ s) diagram. Enthalpy versus entropy (/ —s) diagram. or Mollier diagram. Pressure versus enthalpy. (P — A) diagram.78 ENGINEERING THEAMODYNAMICS THROUGH EXAMPLES Example 3.9 Explain the terms — ‘saturated liquid’ and ‘saturated vapor’ : Solution ; A liquid which is in equilibrium with its own vapor ata specified temperature / pressure is called a saturated liquid. That is a liquid at its boiling point at specified pressure is a saturated liquid. A vapor which is in equlibrium with its own liquid at a specified temperature / pressure is called saturated vapor. That is a vapor at its condensing temperature at specified pressure is a saturated vapor. It is known that at standard atmospheric pressure water boils at 100°C generating its own vapor. Hence, at standard atmospheric pressure, water at 100°C is a saturated. liquid. The steam or water vapor which is in equilibrium with boiling water at 100°C (at standard atmospheric pressure) is at its condensing temperature and hence it is saturated vapor. Example 3.10 How many thermodynamic degrees of freedom are there fora pure substance existing as (a) saturated liquid and (b) saturated vapor ? Solution : . (a) According to the Gibbs phase rule, the thermodynamic degrees of freedom (F) are given by FoC+2-P Where C is the number of components and P is the number of phases. For a pure substance C= 1. If the substance is existing as saturated liquid, it is. in equilibrium with its own vapor ( the quantity of vapor may be negligible). Hence P=2. Application of the phase mule gives F=C +2-P=1+2-2=1.Hence only one intensive property can be specified for the complete description of the state of the system. Therefore, one can specify either pressure (P) or temperature (7). For example, the system is saturated liquid at standard atmosphere pressure (P= 101.325 kPa). Then the temperature at which the saturated liquid is existing is 100°C. On the other hand if the temperature of the saturated liquid is specified as 100°C then the system pressure is one standard atmosphere. (b)Saturated vapor implies that it is = | and P= 2. Therefore, application of the phase rule gives F=C+2-P=1 +2-2= 1. Hence, one can specify either temperature (7) or pressure (P). in equilibrium with its own liquid. Hence Example 3.11 Explain the terms ‘saturation temperature’ and ‘saturation pressure’.PROPERTIES OF SIMPLE COMPRESSIBLE FLUIDS 73 Solution : The temperature at which a liquid boils (or in equilibrium with its own vapor) at a specified pressure is called saturation temperature . The pressure, at a specified temperature, at which the liquid boils (or in equilibrium with its own vapor) is called saturation pressure, We know that at standard atmospheric pressure (P = 101.325 kPa), water boils at 100°C. Therefore, at P = 101.325 kPa, the saturation temperature of water is 100°C. At 100°C, the saturation presure of water is 101.325 kPa. Sometimes, the saturation presure is called as vapor pressure. Example 3.12 What is quality or dryness fraction ? Sohition : A mixture of saturated liquid and saturated vapor is described by specifying its quality (X) or dryness faction . The quality is defined as the ratio of the mass of saturated vapor to the total mass of the mixture. That is, mass of saturated vapor wality = q mass of mixture m, or = —_— my +m, where wi = mass of mixture m, = mass of saturated liquid m,, = mass of saturated vapor Example 3.13 Express the specific / molar volume of a mixture in terms of the quality of the mixture. ’ Solution Since volume is an extensive property, it is additive. That is, the total volume of a mixture is the sum of the volumes of saturated liquid and saturated vapor. Lety, and v, denote the specific / molar volume of saturated liquid and saturated vapor, respectively. Then the total volume (V) of a mixture of mass (nt) is given by Veunv = my, ptm, Ve (A) my, my, ep My or vs + m m -X)v/+ Xv,ENGINEERING THERMODYNAMICS THROUGH EXAMPLES or ve, +X (v,—¥)= 9+ Xv, Where v = specific yolume of mixture vg =¥, —¥y = Change in specific volume due to vaporization. Eqn. (A) can be rewritten as my = {mt m,) v= my, + My, or (B) fig ¥- Vy Eqn. (B) is commonly known as the lever rule. Similar relations can be used to describe any extensive property (like internal energy u, enthalpy /, entropy s) of a mixture in terms of its quality, X. Example 3.14 What is triple point ? Fora pure substance how many degrees of freedom are there at the triple point? Solution + The state at which all the three phases — solid, liquid and vapor coexist in equilibrium is called the triple point. At the triple point , C = 1; P = 3 and application of the phase rule gives F = C +2 -— P=1+2-3 = 0. Hence, the number of degrees of freedom at the triple point is equal to zero. In other words the triple point is invariant (F'= 0), One cannot arbitrarily assign either temperature or pressure for the triple point. The triple point exists at a definite pressure and temperature. For example, the triple point of water is P = 0.611kPa and #=0.01°C. Example 3.15 What is critical point 7 Solution ; Critical point represents the highest temperature and pressure above whicha liquid cannot exist.At the critical point the liquid and vapor are indistinguishable. ‘That is, the propertics of saturated liquid and saturated vapor are identical at the critical point, The temprature and pressure at the critical point are called critical temperature (7,) and critical pressure (P.). If a vapor or gas is to be condensed (or liquified) at constant temperature by the application of pressure, its temperature must be below the critical temperature. Similarly, if a gas is to be liquified by cooling at constant pressure its pressure must be below the critical pressure.PROPERTIES OF SIMPLE COMPRESSIBLE FLUIDS a1 Example 3.16 Suppose energy is continuously transferred as heat at constant pressure to a solid till it completely converts into vapor. Represent the path followed by the system (solid) on a temperature versus volume diagram. Solution : Fig.E 3.16. Temperature~volume diagram at four different pressures P,>P,>P,>P If energy is transferred as heat at constant pressure P, to a solid at state A, its temperature and specific volume increase and follows the path A B as shown in Fig.E 3.16. At state B, the solid starts melting while the temperature remains constant, tll it reaches state C where it completely exists as liquid. The segment BC represents the fusion process. On further heating, the specific volume and temperature of the liquid increase and the system follows and path CD. At state D the liquid stants vaporizing. With continued heating, more and more of liquid vaporizes while its temperature remains constant and the path followed by the system is represented by DE in Fig.E 3.16. The segent DE represents the vaporization process. At state D, the liquid is available as saturated liquid. At state E all the liquid is completely vaporized. The vapor at state Eis called saturated vapor. On further heating the vapor follows the path E F. If similar experiments are made at higher pressures P, fo P, (P,> P,> P,> P,) and the results are represented on the same diagram, they will appear as shown in Fig.E 3.16. Example 3.17 ‘What is meant by superheated vapor ?a2 ENGINEERING THERMODYNAMICS THROUGH EXAMPLES: Solution : A vapor existing at a temperature above the saturation temperature at a specified pressure is called superheated vapor. For example steam at 101.325 kPa and 150°C is a superheated vapor, since at the specified pressure P = 101,325 kPa the saturation temperature of water is 100°C and the vapor is available at 150°C which is above the saturation temperature. Example 3.18 What is subcooled liquid or compressed liquid ? Solution : A liquid at a temprature below its saturation temperature, at a specified pressure, is called subcooled liquid or compressed liquid. Subcooled liquid implies that it is existing at a temperature which is less than the saturation temperature, at the specified pressure. The term compressed liquid implies that the liquid is existing at a pressure which is greater than the saturation pressure, at the specified temperature. Example 3.19 Sketch the pressure-volume diagram for a pure substance and indicate the various regions on it. Solution : Constant quality lines. Fig.E. 3.19, Pressure versus volume diagram for a pure substance.PROPEATIES OF SIMPLE COMPRESSIBLE FLUIDS 8 The curve AB represents the saturated liquid. Saturated vapor is represented by the curve BC. The point C denotes the critical point. The isotherms are shown by the curves 7, to 7, (7, > T, > T, > T,) The regions denoted by Land V correspond to subcooled liquid and superheated vapor, respectively. The region enclosed by the dome ACB denotes the two phase region where mixtures of saturated liquid and saturated vapor are present. The constant quality lines are indicated by dashed lines and these constant quality lines merge at the critical point. The points D and E represent the saturated liquid and saturated vapor which are in equilibrium with each other. The point M, lying on the line segment DE, in the two phase region, denotes a mixture of quality X. Example 3.20 Suppose a constant volume vessel is initially filled with a small quantity of saturated liquid and the remaining volume is filled with saturated vapor at a given temperature and the vessel is heated. Trace the path followed by the system (material contained in the vessel) on a P-v diagram. Show the path on the same P—v diagram had the vessel been filled with a large quantity of saturated liquid and the remaining volume with saturated vapor. Solution : ‘The volume of the vessel as well as the mass of material in the vessel remain constant during heating. Hence, the specific volume of the material remains constant. In other words, the system follows a constant volume process. If the vessel is filled with a small quantity of saturated liquid, the quality (X) of the initial mixture is large. That is the initial state is close to the saturated vapor curve as shown by A in Fig.E 3.20. As energy is transferred in the form of heat to the system, its temeperature and pressure increase at constant volume. The path followed by the system is as shown by ABCD. Finally the system ends up in the superheated vapor state | (point D). Fig.E 3.20. P- v diagram showing constant volume heating process,ENGINEERING THERMODYNAMICS THROUGH EXAMPLES At state B, the quality of the mixture is X, which is greater than X,,. At state C, the substance is saturated vapor. That is during heating, the liquid vaporizes increasing its quality from X, to X, and at state C, X= 1. With further heating the system reaches state D, If the vessel is initially filled with a large quantity of saturated liquid, the quality of the mixture is low (X,) and the system is in state 1, During the constant volume heating, the system follows the path 1234 as shown in Fig.E 3.20. With continued transfer of energy as heat at constant volume, the liquid expands, its quality decreases (X, < X,) and occupies the entire vessel at state 3 where it is available as saturated liquid (X, = 0). With further heating, the system reaches state 4, where it is available as subcooled liquid or compressed liquid. The isotherm passing through state 4 is shown as T,. The saturation pressure corresponding to T, is shown as P, The system is at pressure P, which is greater than P, and hence the system at state 4 exists as a compressed liquid. Example 3.21 Suppose a closed and rigid vessel is initially filled with a mixture of saturated liquid water and saturated water vapor at 100 kPa. On transferring energy as heat, the water is found to pass through the critical point . Determine the ratio of the volume of saturated vapor to the volume of the saturated liquid with which the vessel is initially filled, At 100 kPa, = 0,001 043 4 m3 / kg and = 1.694 m*/ kg. The critical volume of water is 0.003 17 m'/ kg. Solution = Saturated liquid Critical point ed v Ye v, Fig.E 3.21. P-y diagram showing the constant volume heating pracess which takes the system through critical point. As the vessel is rigid, its volume remains constant, Since the vessel is closed and the total mass of mixture remains constant the system follows a constantPROPERTIES OF SIMPLE COMPRESSIBLE FLUIDS 85 volume process. It is given that the system passes through the critical state on heating. Therefore, the specific volume at the critical point is equal to the specific volume of the mixture. That is Vs y= Xv, + (EX) vy {A) Where vy, is the specific volume of the mixture. The path follwed by the system is shown as M N on a P-v diagram in Fig.E 3.21. The point M denotes the initial mixture at 100 kPa and the points F and G denote the saturated liquid and saturated vapor, respectively at 100 kPa, Substituting the given values in Egn. (A), we get 0.003 17 = 1,694 X + (1— X) 0.001 043 4 or X= 0:00317- 0.001043 4 95651079 1.694—0.001043.4 Volume of saturated vapor 7,¥, _ (m,/my, Xv, Volume of saturated liquid — my (iy mv, (=X _ 1256x107 «1.694 (1= 1.256 x 107*)0.001 043 4 Example 3.22 The pressure-volume-temperature relationship for a substance can be conveniently shown on a P -v~ T diagram. Sketch the P- v- T diagram for a substance which contracts on freezing. Solution : Fig.E 3.22 shows the P - v—- T diagram for a substance which contracts on freezing. Many substances follow the trend shown in the figure. However, there are some exceptions like water which expands on freezing. The solid, liquid and vapor phases appear as surfaces. These single phase regions (marked as S, L and V) are separated from the two phase regions (S + L), (S + V) and (L_+ V) by surfaces which represent a two phase mixture. For example, the solid and liquid regions are separated by a solid—liquid surface. Similarly, the liquid and vapor regions are separated by a tiquid—vapor surface. Any state denoted by a point lying on a line separating the single phase region from a two phase region is called Saturated. It can be observed from Fig.E 3.22 that the isotherm shows a discontinuity at the saturated state . For example the isotherm 1234 is discontinuous at 2 and 3. The liquid existing at state 2 is called saturated liquid while the vapor at state 3 is called saturated vapor.ENGINEERING THERMODYNAMICS THROUGH EXAMPLES: v temperature line Fig.E 3.22, P-v—T diagram for a substance which contracts on freezing. Example 3,23 Sketch a phase (P versus 7) diagram for water and indicate the solid, liquid and vapor regions on it. Explain how this diagram differs from the phase diagram of other substances. Solution ; diagram for water is shown in Fig.E 3.23 in which the regions of id, liquid and vapor are indicated. The single phase regions are separated from each other by saturation lines. For example, the solid and liquid regions are separated by the fusion curve 72. Along the fusion curve both solid and liquid phases coexist in equilibrum. It can be observed that the slope of the fusion curve is negative. oP als 0 That is, which shows that the melting point of ice decreases with increasing pressure. The sublimation curve IT separates the solid region from the vapor region, while the vaporization curve TC separates the liquid region from the vapor region. Along the sublimation curve the solid and vapor phases coexist in equilibrium while the liquid and vapor phases coexist in equilibirium along the vaporization curve. The phase diagram shown in Fig.E 3.23 represents the phase behavior ofPROPERTIES OF SIMPLE COMPRESSIBLE FLUIDS a7 substances (like water, bismuth and antimory) which contract on melting, that is, the specific volume of the liquid is smaller than the specific volume of the solid The state T represents the triple point where all the three phases—solid, liquid and vapor coexist in equilibrium. The state C represents the critical point where the properties of liquid and vapor are identical and they cannot be distinguished from one another. For all other substances the slope of the fusion curve will be Positive (as shown by T 2’ on the diagram) which indicates that the melting point increases with increasing pressure. T FigE. 3.23. Phase diagram for water. Example 3.24 An anomolous behavior of water is observed on the phase diagram. That is, the slope of the fusion curve is negative for water whereas forall other substances the fusion curve has a positive slope. Give two examples where this anomolous behavior is found to be advantageous. Solution. : When water freezes into ice, its specific volume increases or density decreases. Hence ice floats on water. In cold countries the water in the lakes and sea starts freezing and the ice thus formed floats on water. The floating ice acts as an insulating material and does not expose the water at the bottom layers to the cold atmosphere thus preventing further freezing of water at the bottom layers. Therefore, the acquatic life can survive in the water. The melting point of ice decreases with increasing pressure. This phenomenon is taken to advantage by ice skaters. In the cold countries as well as in some parts of north India, like Simla, Jammu and Kashmir the water in the lakes freeze into ice at temperatureENGINEERING THERMODYNAMICS THROUGH EXAMPLES: han O°C. At atmospheric pressure, ice does not melt below 0°C. The ice skate: usually tapered at the bottom and under normal conditions of use, the area of contact between the skates and ice is very low, When a person stands on the skates, he/she exerts enormous pressure on the ice. Then the ice below the skates starts melting because of the applied pressure. The melting ice provides a thin layer of water between the ice surface and skates which acts as a lubricant which is turn helps in smooth gliding. Example 3.25 Suppose a closed and rigid vessel is initially filled with a (a) large quantity of saturated liquid water and the remaining volume is filled with saturated water vapor. (h) small quantity of saturated liquid water and the remaining volume is filled with saturated water vapor and energy is transferred as heat to the vessel. Since the volume of the vessel and the quantity of water remain constant, the water follows a constant volume process. Sketch the constant volume paths followed by water, in both the above cases, on a phase diagram. Solution : (a) If the vessel is filled with a large quantity of saturated liquid water and heated at constant volume the path followed by water is shown as 1234 on a P_v diagram in Fig.E 3.20. At states | and 2, both the liquid and vapor phases coexist and hence these states lie on the vaporization curve ona phase diagram. State 3 represents saturated liquid and hence this state also lies on the vaporization curve. The state 4 represents liquid and hence it lies in the liquid zone. Since the compressibility of liquid is very low, the rise in pressure with temperature will be very high and hence the slope of 3-4 is large. The constant volume path 1-2-3-4 is shown in Fig.E 3.25 on a phase diagram. P 7 Fig. 3.25. Representation of constant volume lines on a phase diagram.PROPERTIES OF SIMPLE COMPRESSIBLE FLUIDS a (by When the vessel is filled with a small quantity of saturated liquid water and heated at constant volume, the path fallowed by water is shown as ABCD on a P-v diagram in Fig.E 3.20. The states A, B, and C, lie on the vaporization curve while the state D lies in the vapor region. The constant volume path followed by water is shown as ABCD on a phase diagram in Fig.E 3.25, Example 3.26 Represent the following processes on a phase diagram. (a) Constant pressure heating of liquid water to produce superheated vapor. (b) Isothermal vaporization of liquid water to produce superheated steam. (c) Liquid water is converted to superheated steam without observing the phase transition. That is the vaporization of liquid cannot be detected during phase change. Solution : b Super critical fluid Fig.E 3.26. Phase Diagram. (a) The initial state of liquid water is indicated as | in Fig.E 3.26. If energy is added as heat at constant pressure to liquid at state 1, the temperature of the liquid increases till it reaches state A, where it is available as saturated liquid. If energy addition is continued, vaporization occurs and the temperature and pressure remain constant tll all the liquid is converted into saturated steam. The state A represents both the saturated liquid and saturated vapor. With continued addition of energy water reaches state 2, which is superheated vapor. (b) If liquid water at state | is maintained at constant temperature and the pressure is reduced, it follows the path 1B3. State B represents saturated liquid as well as saturated vapor and state 3 denotes superheated vapor,ENGINEERING THERMODYNAMICS THROUGH EXAMPLES (c) If liquid water at state 1 is subjected to a process path indicated by 1D4 as shown in Fig.E 3.26, it is not possible to observe the phase change at any stage during the course of the process. The process path passes through the supercritical fluid region. It is always possible to convert a liquid into vapor or vice -versa without observing phase transition, by taking the fluid through the supercritical fluid region. Example 3.27 Sketch the phase diagram fora substance that expands on freezing and indicate the regions of subcooled liquid and superheated vapor. Solution : The phase diagram for a substance like water which expands on freezing in shown in Fig-E 3.27. The liquid existing at state | in Fig E 3.27 is called subcooled Jiquid. The liquid at state | is characterized by pressure P, and temperature 7,, At nn Oo Fig.E 3.27. Phase diagram for a substance thai expands on freezing. the specified pressure P, the saturation temperature of the liquid is T., Since the liquid at state 1 is at a temperature 7, which is less than the saturation temperature 7, it is called subcooled liquid. This state can be achieved by cooling the saturated liquid at state a to a temperature T, < 7, . The liquid at state 1 can also be called as compressed liquid since at the specified temperature 7, the liquid exists ata presure P, which is greater than the saturation pressure P,,, This state can be achieved by compressing the saturated liquid at state b to a pressure P, > P,. Similarly, the vapor at state 2 is at a temperature 7, which is greater than the saturation temperature 7, at the specified pressure P,. Hence the vapor at state 2 is called super heated vapor. Usually the termPROPERTIES OF SIMPLE GOMPRESSIBLE FLUIDS 1 superheating is used if the temperature of a vaporis increased at constant pressure. For a pure substance exsisting in two phases liquid and vapor-the saturation pressure is usually referred as vapor pressure. The temperature al which a given liquid boils at standard atmospheric pressure (101.325 kPa) is called the normal boiling point. Example 3.28 Name a few drawbacks associated with the graphical representation of thermodynamic data, Solution. : ‘The drawbacks associated with the graphical representation of thermodynamic data are: 1. The values of the properti cannot be read accurately. 2. Sometimes it is necessary to interpolate the data leading to loss of accuracy, since the data is usually presented at some selected values of the independent variables only. 3. Quite often it is necessary to have a knowledge of the partial derivatives of the thermodynamic properties and such information is not rea available on thermodynamic diagrams. The estimation of the partial derivatives of thermodynamic properties from diagrams is quite difficult and invariably the estimated values can be used as approximate values only and are not accurate. 4. The number of properties that can be presented on a diagrams is limited. Any attempt to increase the number of properties renders the diagram unreadable and leads to confusion. Example 3.29 Suggest an alternative method of representing the thermodynamic data, which. is likely to overcome some of the drawbacks associated with the graphical representation, OR List the advantages of representing the thermodynamic data in » tabular form compared to the graphical representation. Solution : An alternative method of representing the thermodynamic data of pure substances is to present the data in tabular form. The tabular representation of data overcomes some of the drawbacks associated with the graphical representation of the same data. The advantages associated with the tabular representation of data are given below ,ENGINEERING THERMODYNAMICS THROUGH EXAMPLES 1, The values can be read accurately, . The data can be listed in fine increments of the independent variables. wot . There is no limitation on the number of properties that can be presented in a tabular form. Example 3.30 Describe the most convenient and widely used format for the tabular representation of thermodynamic data of saturated steam. Solution The important thermodynamic properties like Pv, 7, u, hand s for saturated liquid and saturated vapor are presented in a tabular form, Such tables are available for water, ammonia, sulfur dioxide, carbon dioxide, freons etc. which are commonly used as working fluids in heat engines and refrigerators. In general, the format of all these tables is similar. Hence, it is enough if a representative table for one fluid is described. Since steam is extensively used in power plants and in several industries and an exact equation of state which is applicable over wide ranges of temperature and pressure is not available, the steam tables are described below. If a single component simple system exists in two phases, say liquid and vapor, then the system (the substance under consideration) has only one degree of freedom. That is, only one independent thermodynamic property (either P or T), can be specified for the complete specifiction of the state of the system. If the temperature Tis chosen as the independent variable , then the system has definite values for all other thermodynamic properties. The most convenient and widely used format of the saturated steam (Temperature) table is as given in table for Example 3.30 (page 93). Example 3.31 What is the reference state chosen for tabulating the thermodynamic properties of water in the steam tables ? Solution : The selection of the reference state for the purpose of tabulating the thermodynamic properties of a substance is quite arbitrary and itis governed by convenience only and nat by any law. The selected reference states differ from substance to substance. By convention, the saturated liquid water at its triple point (0.01°C and 0.6113 kPa) is chosen as the reference state while tabulating the thermodynamic properties of steam. The specific (molar) intemal energy (u)PROPERTIES OF SIMPLE COMPRESSIBLE FLUIDS: 33 Table for Example 3.30. Temperature Pressure? Specific volume Specific enthalpy Specific entropy we) _ (kPa) dm'vkg) (kJ/kg) kJ/kg Ky Sat.liquid Sat. Vapor Sat. liquid Sat. vopor Sat. liquid ‘Sat. vapor " * hy a, wi 0 0.6108 — 0.001 0002 206.3 0.04 2501.6 0.0002 9.1577 0.01 0.6113 0,001 0002 206.15 0,000 61 2501.4 0.0000 9.1573 100 101,33 0,001 043 7 1.673 419.06 2676.0 1.3069 7.3554 200 1554.9 0,001 1565 0.1272 852.37 2790.9 2.3307 6.4278 374.15 22120.0 0.003 17 0.003 17 2107.4 2107.4 4.4429 4.4429 Table for Example 3.33 Pressure P ‘Temperature Speeific volume Specific enthalpy Specific entropy (kPa) we) (m’ikg} (kJ/kg) (kJ/kg K) Sat. liquid Sat. Vapor Sat. liquid Sat. vapor Sat. liquid Sat. vapor % " hy 4, 5 5, 0.6113 0.01 0,001 0002 206.15 0.00061 2501.4 0.0000 9.1573 1 6.9828 «60,001 0001 = 129.20 29.34 2514.4 0.1060 8.9767 3 32.898 0,001 005 2 28.19 137.77 2561.6 0.4763 8.3960 10 45.833 0.001 0102 14.67 191.83 2584.8 0.6493 8.1511 100 99.632 0,001 043 4 1.694 417.54 2675.4 1.3027 7.3598 200 120.23 0,001 6608 0.8854 504,70 2706.2 1.5301 7.1268 22120 374.15 0.003 17 0.003 17 2107.4 2107.4 4.4429 4.4429 eSENGINEERING THERMODYNAMICS THROUGH EXAMPLES and the specific (molar) entropy (s) of saturated liquid water at the triple point have been arbitrarily assigned a value of zero in the steam tables, Example 3.32 State the ranges of temperature and pressure as well as the states for which the thermodynamic properties of saturated steam are tabulated in the steam tables. Solution : All the steam tables present the thermodynamic properties of saturated liquid and saturated vapor starting from the triple point (0.01°C and 0.6113 kPa) to the critical point (374.15°C and 22.12 MPa). Since the properties of water at O°C are quite often needed in the thermodynamic calculation, the properties of saturated liquid and saturated vapor at this temperature are also tabulated in the steam tables, Example 3.33 Describe the format of the saturated steam tables if one choases to use the pressure as the independent variable for the specification of the state of the saturated liquid or saturated vapor. Solution : IF the pressure P is chosen as the independent variable for the description of a two phase single component system (liquid and vapor phases coexisting ina state of equilibrium), then the system has definite values for all other thermodynamic properties. The widely used format of the saturated steam {pressure} tables is given on page 93. The data presented in the saturated steam (temperature) and saturated steam (pressure) tables is the same but the format differs from each other. Example 3.34 In thermal power plants and in process industries one deals with superheated steam, that is steam at a temperature which is above the saturation temperature. Describe the most widely used format for presenting the thermodyanmic properties of superheated steam. Solution : The superheated steam exists in only one phase, Hence two independent variables-pressure (P) and temperature (7)- are to be specified for complete de- ‘Seription of the state of the superheated steam. The most convenient and widely ‘used format for presenting the thermodynamic properties of superheated steam is given below.PROPERTIES OF SIMPLE COMPRESSIBLE FLUIDS Pressure P(bar) (Saturation temperature °C) 0.2 (60,09) (99.63) 2 (120.23) 20 (212.37) Example 3.35 vim'vkg) htkIfkg) (kk K) 8.585 2686.3 8.1261 1.6960 2676.2 7.3618 ‘Temperature (°C) 200 10.507 2879.2 8.5839 2.1720 2875.4 7.8349 1.0804 2870.5 7.5072 13.219 3076.4 8.9618 2.6300) 3074.5 8.2166 1.3162 3072.1 T8997 0.1255 3025.0 6.7696 Freon-12 (dichloro difluoro methane CIF, } and ammonia are used as refrigerants, Specify the reference state which is normally adopted for tabulating the thermodynamic properties of these substances,ENGINEERING THERMODYNAMICS THROUGH EXAMPLES Solution By convention the saturated liquid at—40°C is chosen as the reference state for tabulating the thermodynamic properties of refrigerants. The internal energy (u,) and entropy (s,) of saturated liquid at 40°C have been arbitrarily assigned a value of zero. Example 3.36 Does the arbitrary selection of the reference state for tabulating the thermodynamic properties of substance affect the thermodynamic analysis of processes ? Solution ; The choice of reference state does not affect the thermodynamic analysis of Processes since in thermodynamics one is concerned with the changes in the thermodynamic properties of the substances while they undergo a process. Example 3.37 What is the saturation temperature of water at 0.5 bar pressure ? What is the saturation pressure of water at 130°C 7 Solution = From the saturated steam tables (pressure) given in the Appendix-I one can read the saturation temperature as 81.345°C at 0.5 bar pressure. From the saturated steam (Temperature) tables given in Appendix -2, one can read the saturation pressure as 2.7013 bar. Example 3.38 The domestic pressure cookers maintain a pressure of 2 bar while food is cooked in it. Determine the temperature at which water boils in a domestic pressure: cooker, Solution : The boiling point of water in a domestic pressure cooker is equal to the saturation temperture at 2 bar. From the saturated steam tables (Pressure) given in the Appendix~ 1, one can read the saturation temperature of water at 2 bar pressure as 120.23°C. Example 3.39 Determine the specific volume of wet steam of quality 0.7 at 200°C.PROPERTIES OF SIMPLE COMPRESSIBLE FLUIDS 7 Solution : Read the following values from the saturated steam (Temperature) tables given in Appendix —2. ¥, = 0.001 1565 mikg i v= 0.1272 mfkg The specific volume of a two phase mixture can be calculated from the relation v= Xv, + (1-X) v, where X = quality of mixture. v=0.7 (0.1272) + 0.3 (0.001 156 5) = 0.0894 mi/kg Example 3.40 Determine the quality of wet steam at 200°C with a specific volume of 0.095 m/kg. Solution : From steam tables (Appendix—2) for steam at 200°C we get vy =0.001 1565 mvkg and v, = 0.1272 m/kg we know that v= Xv, +(1-X) Me Subsitituing the values of v, v, and v,in the above relation we get. 0.095 = X ( 0.1272) + (1 - X) 0.001 1565 or 0.095 — 0,001 156 5 = (0.1272 — 0.001 156 5)X 0.095 -0.001 1565 = 0.7445 0.1272 = 0,001 1565 or Therefore, the quality (X) of the wet steam is 0.7445. Example 3.41 ‘Wet steam at 6 bar has a specific volume of 0.29 m'/kg. Determine the specific volume if wet steam of the same quality is maintained at 3 bar. Solution Read the following data from the steam tables given in Appendix—1. Saturated steam at 6 bar : v= 0.001 1009 mi/kg ; v, = 0.3155 m/kg. Saturated steam at 3 bar : v,= 0.001 0735 mivkg ; », = 0.6056 mivkg, we know that va Xv, + (IX) vy (A) Egn (A) can be rearranged as xo ote (By MeOENGINEERING THERMODYNAMICS THROUGH EXAMPLES Substituting the values of ¥, vy and v, at 6 bar in Eqn. (8), we get = 0.29 - 0.001 1009 = 0.9188 0.3155 -0.001 1009 The specific volume of wet steam of quality 0.9188 at 3 bar is calculated from Eqn. (A) by substituting X = 0.9188 and the values of 7 and vat 3 bar. v= 0.9188 (0.6056) + (1— 0.9188) 0.001 073 5 = 0.5565 mvky Example 3.42 A vessel of volume 2m’ contains wel steam of quality 0.8 at 210°C. Determine the masses of liquid and vapor present in the vessel. Solution : The following data can be read from the steam tables (see Appendix — 2) at 210°C v= 0.001 172 6 mkg; v, = 0.1042 mikg The specific volume of wet steam of quality (X) 0.8 is given by v= Xv, + (I-X) v,= 0.8 (0.1042) + 0.2 (0.001 172 6) = 0.0836 mkg v 2 SS Of St ii = — mass of steam (m1) in the vesse | y * 0R36 = 23.923 kg where V = volume of the vessel Mass of vapor (m,) = mX = 0.8 x 23.923 = 19.138 kg Mass of liquid m, = (1 ~ X) m= 0.2 * 23.923 =4.785 kg Example 3.43 Determine the volume occupied by 1 kg of steam at the following conditions (a) P=0.4 bar: t= 300°C (b) P= 4 bar ; r= 300°C and (c) P= 10 bar ; r= 500°C Solution : The following values can be directly read from the superheated steam tables given in Appendix - 3 (a) P= 0.4 bar and 1 = 300°C : v = 6.6065 m¥kg (by P= 4 bar and t= 300°C : v = 0.6549 miskg (c) P= 10 bar and = 500°C : vy = 0.3540 m/kg>ROPERTIES OF SIMPLE COMPRESSIBLE FLUIDS 99 Example 3.44 Determine the specitic volume of steam at 25 bar and 330°C Solution + The steam tables given in Appendix — 3 does not have enteries at 25 bar and 330°C. If the data is not tabulated in close intervals, it is recommended to estimate the required data by making use of linear interpolation. First, [et us calculate the specific volume at 25 bar pressure at temperatures 300°C and 400°C as indicated below. Now read the following data from steam tables ( seeAppendix — 3), P= 24 bar and 1 = 300°C: v 103 36 mvkg P= 26 bar and 1 = 300°C : v = 0.094 83 mivkg Therefore, the specific volume (v,) at P = 25 bar and 1, = 300°C can be calculated as. _ 0.103 36 +0.09483 1 3 0.099095 mivkg ¥, Similarly. we read the following values also P= 24 bar and r= 400°C : v = 0.125 22 mivkg P=26 bar and = 400°C : v=0.115 26 mvkg Therefore, the specific volume (v,) at P = 25 and t, = 400°C is given by. 0.125 22+0,115 26 = 2 Having determined the specific volumes at 300°C and 400°C at a pressure of 25 bar, we can again use the method of linear interpolation to determine the specific volume at P = 25 bar and ¢ = 330°C as shown below. The specific volume (v) at temperature 7 is given by (22 }- 4) = 0.12024 miskg 0.099 095 + (0:12024- 0.099.095) 435 _ 309) (400-300) = 0.105 439 mk Example 3.45 List some of the drawbacks associated with the tabular representation of thermodynamic properties of a substance.ENGINEERING THERMODYNAMICS THROUGH EXAMPLES Solution ; Some of the drawbacks associated with the tabular representation of thermodynamic properties are given below. 1. The data cannot be presented in fine increments of the independent variables and for all the substances as the data is likely to occupy several volumes. 2. In thermodynamic analysis quite often one is interested in the values of the partial derivatives of the thermodynamic properties. Accurate values of these partial derivatives cannot be obtained from the data if it is presented in tabular form. 3. Since the data is usually presented in finite increments of the independent variables, some times it is necessary to interpolate the data. The accuracy of the interpolated values is usually poor. Example 3.46 What is an equation of state ? Solution + A mathematical expression of the type f{Ry,7) = 0 which describe the P- v -T behavior of substances is called an equation of state. Such a relation is called the mechanical equation of state. For a single component simple system there are three equations of state. They are (a) Mechanical equation of state (b) Thermal equation of state and (c) Chemical equation of state. It may be noted that all the equations of state of a substance are not independent and there exists. relationship among them. In general an equation which expresses the intensive parameter as a function of the extensive parameters is called an equation of state. A detailed discussion of the equations of state is beyond the scope of this book and hence we focus our attention on mechanical equation of state only. Example 3.47 State the Boyle‘s law and Charles law. Solution ; Boyle’s law states that the molar volume (v) of a gas varies inversely with pressure (P) when tempertaure (7) is held constant, That is, I vee or Py =constant {at constant Temperature). Charles law states that (a) the molar volume of a gas is directly proportional to temperature when the pressure is held constant. That is v o T (at constantPROPERTIES OF SIMPLE COMPRESSIBLE FLUIOS 101 pressure) and (/) the pressure exerted by a gas is directly proportional to temperature when the volume is held constant. That is P 2% 7 (at constant volume). Example 3.48 What is an ideal gas equation of state ? What assumptions are made in deriving the ideal gas equation of state from the kinetic theory point of view and how does one justify these assumptions ? Solution : The ideal gas equation of state is given by Pv = RT or PV = nT where v = molar velume, V = total volume, 2 = number of moles and R = universal gas constant which is equal to 8.314 J Amol K or 8.314 kI/ kmol K. Based on the following assumptions, the ideal gas equation of state can be derived through the kinetic theory of gases, 1. The volume occupied by the gas molecules is negligible compared to the volume available for free motion. 2. The molecules are independent of each other and do not exert any attractive forces. Atnormal temperature and pressure the number of molecules per cubic metre are approximately 2.4 x 10*5, Hence, the volume available per molecule is approximately 4 x 10-74 m*. The diameter of a molecule is approximately 2 x 107 mand hence the volume of each molecule is approximately 4x 10°27 m3. Hence the volume occupied by the molecule is about 1/1000 of the volume available for free motion . Therefore, it is reasonable to assume that the molecules do not occupy any volume. The volume available per molecule is 4x 10-4 mm or the distance between two adjacent molecules is approximately 10° m whereas the diameter of the molecule is 2 x 107! m. Thus, the distance between two molecules is 50 times the diameter of a molecule. Hence it is reasonable to assume that a molecule does not exert any attractive force on other molecules. Example 3.49 Is the ideal gas equation of state applicable to all gases and at all temperatures and pressures ? Does it represent the actual P~v— 7 behavior of gases ? Solution : ‘The ideal gas equation of state is applicable only at low densities where the assumptions made in deriving it, through the kinectic theory of gases, can be justified. The ideal gas law is only an approximation or idealization to the behavior102 ENGINEERING THERMODYNAMICS THROUGH EXAMPLES of gases. It is applicable at low pressures and high temperatures where the density is sufficiently low, In general the P~v-T behavior of real gases differs from that predicted by the ideal gas law, Example 3.50 It is desired to store 28 kg of nitrogen at 14 MPa pressure and 27°C in a eylinder. Assuming that nitrogen behaves like and ideal gas determine the size of the cylinder. Solution : The ideal gas equation of state is given by. PV=nRT nRT Hene Vs lence: P tity of nit = = 10*mol Quantity of nitrogen = Bx — (molar mass of nitrogen. = 28 x 10“ kg/mol) ‘Therefore volume of the cylinder, nRT _ 10° x 8.314% 300 V=—=———_— = 0. 3 ? Tax 0.1782 m Example 3.51 AO.| m* cylinder is charged with ethane ( C,H, ) to a pressure of 120 bar at 27°C. Assuming that ethane behaves like an ideal gas, estimate the mass of ethane in the cylinder. Solution : Molar mass of ethane ( C,H, } = 30x 10“? kg/ mol = 120 bar = 120 x10 5 Pa , P= 273 + 27 = 300 Kv =0.1 m* We know that for an ideal gas PV=nRT or _ PV _120x10° x0. RT = 8.314300 Mass of ethane in the cylinder = 481.12 x 30 x 107 = 14.434 kg = 481.12 molPROPERTIES OF SIMPLE COMPRESSIOLE FLUIDS 103 Example 3.52 {a) Suppose it is desired to charge 15 kg of ethane at 300 K into a cylinder of volume 0.08 m’, determine the pressure to which the cylinder is to be charged. (b) If 20 kg of ethane is charged into a cylinder of capacity 0.15 m3 and the cylinder is held ata pressure of 15 MPa, determine the temperature of the gas in the cylinder. Assume that ethane behaves like an ideal gas. Solution = (a) Given data: T= 300 K ; V= 0.08 m* 1S Quantity of ethane = 15 kg oxo 500 mol (Molar mass of ethane C,H, = 30 x 10" kg /mol) We know that for an ideal gas PV= nT nRT _ 500x 8314x300 vO 008 = 15,589 MPa Therefore, pressure at which the cylinder is to be charged is 15.589 Mpa 20 ib antity of ethane = 20kg = = 666.67 mal (0) Quantiey oFetnane= 288 = O10 P= 15 MPa; V=0.15 m* We know that PV=aART PV 15x10" x0.15 Se 2 05.94 K “r TOR 66667x8314 Therefore, temperature of ethane in the cylinder = 405.94 K = 132.79°C Example 3.53 The Van der Waals equation of stat a modification of the ideal gas law. Name the factors which were taken into account by Van der Waal in modifying the equation of state. Solution + The ideal gas law is only an approximation or idealization to the P= v— 7 behavior of gases and it is applicable at low densities only. The P—v—T behavior of real gases differ from that predicted by the ideal gas law. In 1873 Van der Waals proposed an equation of state which takes into account 1. The unavailable volume for molecular motion, that is the excluded volume andENGINEERING THERMODYNAMICS THROUGH EXAMPLES 2. ‘The attractive forces between the molecules which leads to a reduction in pressure exerted by the gas, while modifying the ideal gas equation of state. Example 3.54 Explain the terms excluded volume and reduction in pressure which were incorporated in the ideal gas equation ef state leading to Van der Waals equation of state. Solution : While deriving the ideal gas law, in the kinetic theory of gases, it is assumed that the molecules do not occupy any volume. In real gases, such asumption is not valid since the molecules do occupy some volume. The Van der Waals equation of state takes into account the volume occupied by the molecules as explained below. The gas molecules are considered to be hard spheres of radius: Then the centre to centre distance between two molecules at the instant of collision is 2r, Therefore, a molecule cannot reach another molocule such that its centre lies within a distance of 2r from the center of the other molecule. That is, the centre of a molecule is excluded from a spherical region, called the sphere of exclusion, of radius 2r from other molecules a shown in Fig.E 3.54. Then, the total unavailable volume or the excluded volume for molecular motion of Ny molecules (Avagadros number) is given by Sphere of exclusion es Fig. 3.54, Sphere of exculsion, 3_ 16 3 3 IO 2ry 3 ftrPROPERTIES OF SIMPLE COMPRESSIBLE FLUIOS 105 In the above equation, the factor 2 is included to avoid counting each pair 4 twice. The actual volume occupied by N, molecules is equal to No ar’. Thus, the excluded volume } is four times the actual volume occupied by the molecules, Therefore, the free volume available for molecular motion is (v — b). In the kinetic theory of gases, the ideal gas equation of state is derived with the assumption that there are no intermolecular forces of attraction between the molecules. In real gases, such an assumption is not valid since there are forces of attraction and repulsion between any pair of molecules.The molecules in the interior of the gas are attracted equally in all directions by the surrounding molecules and hence they do not experience any net attractive and repulsive forces. However, the molecules adjacent to the container wall experience a net inward force, since they are attracted by the surrounding molecules on one side only. Therefore,a molecule adjacent to the container wall exerts less force on the wall. Thus, the observed pressure will be less than the pressure the gas would have exerted in absence of the attractive forces. The reduction in pressure is Proportional to the number of molecules per unit volume (N,/v) in the layer adjacent to the wall and to the number of molecules per unit volume in the next layer, which is attracting. Therefore, the reduction in pressure (P'—P) is given by. 2 , f No) . p-paa(%) or P= Pa v v where P’ js the pressure the gas would have exerted in absence of the attractive forces. P is the observed pressure, ais a constant and a is another constant, If the corrections for excluded volume and attractive forces are incorporated in the ideal gas law, one obtains (3) ¥ which is known as the Van der Waals cquation of state. The constants @ and & appearing in the above equation are called the Van der Waals constants and they depend on the nature of the gas. (v-b) = RT Example 3.55 Sketch the isotherms for a Van der Waals gas on pressure versus volume diagram and explain the significance of the values of volume at T< T,.; T= Ty. and T > T,. where T,, is the critical temprature. Solution : The Wan der Waals equation of state is cubic in volume and in general it gives three values for the volume (v) at a give temperature and pressure. However, for